Additive for imparting ultraviolet absorbency and/or high refractive index to matrix, and resin member using same

ABSTRACT

Provided is an additive for imparting ultraviolet absorbency, or an additive for imparting a high refractive index, which has satisfactory compatibility with a resin serving as a matrix and can maintain high transparency even if added in high concentrations. Also provided is an additive with which the function of imparting both ultraviolet absorbency and a high refractive index can be realized by means of one kind of additive. This additive is represented by the following Formula (I): 
     
       
         
         
             
             
         
       
         
         
           
             wherein at least one of R 1a  to R 9a  is a monovalent sulfur-containing group represented by the following Formula (i-1) or Formula (i-2):
 
 R 10a     m SH  (i-1)
 
 R 11a     n S R 12a —S   p R 13a   (i-2)
 
             wherein R 10a  to R 12a  each represent a divalent hydrocarbon group or the like; and R 13a  represents a monovalent hydrocarbon group or the like.

TECHNICAL FIELD

The present invention relates to an additive for enhancing ultravioletabsorbency or adjusting the refractive index when added to a matrix of aresin or the like, and to a resin member using the additive.

BACKGROUND ART

In regard to optical materials such as optical films and optical moldedarticles, it is important to impart optical functions such asultraviolet absorption and refractive index adjustment, and variousinvestigations have been conducted.

Resin members are deteriorated under the effect of ultraviolet ray andsuffered quality degradation such as discoloration or lowering ofmechanical strength, so that long-term use of resin members isinhibited. In order to prevent such quality degradation or to controlthe wavelength of transmitted light, it has been a general practice toincorporate an inorganic or organic ultraviolet absorber into a resinmember.

Inorganic ultraviolet absorbers have excellent durability such asweather resistance or heat resistance; however, since the absorptionwavelength is determined by the band gap of the compound, the degree offreedom of selection is low, and there are only few compounds that canabsorb even up to the long-wavelength ultraviolet ray region near 400 nm(UV-A, 315 to 400 nm) in the near ultraviolet ray range. Meanwhile,those inorganic ultraviolet absorbers that can absorb long-wavelengthultraviolet ray have absorption of wavelength up to 450 to 500 nm(visible range), and therefore, they cause coloration. Members used insolar cells and the like, development of which has advanced in recentyears, need to be exposed to sunlight for a long period of time in theoutdoors, and deterioration of the properties of the members as a resultof exposure to ultraviolet ray over a long period of time, cannot beavoided. Therefore, there is a demand for an ultraviolet absorber havingexcellent light resistance, which exhibits durability against yellowingof members, and also exhibits a shielding effect for up to the UV-Aregion.

In contrast, organic ultraviolet absorbers are such that since thedegree of freedom of structural design for the absorbers is high,ultraviolet absorbers having various absorption wavelengths can beobtained by devising the structures of the absorbers. On the other hand,organic ultraviolet absorbers are such that when a resin compositionincluding an ultraviolet absorber is heated and then is subjected tomolding and processing, there is a possibility that the ultravioletabsorber may be thermally decomposed, and this decomposition ofultraviolet absorber may lead to decrease in the ultraviolet absorbencyof the resin member, impairment of transparency in the case of atransparent resin member, and contamination of molding and processingapparatuses. Thus, there is a demand for an organic ultraviolet absorberhaving superior heat resistance. Regarding organic ultravioletabsorbers, benzotriazole-based, benzophenone-based, triazine-based,cyanoacrylate-based and salicylate-based ultraviolet absorbers areconventionally known (see, for example, Patent Literatures 1 to 4).

On the other hand, in optical films such as a reflective film, anantireflection film, and a hard coat film, it is required to adjust therefractive index in order to regulate the optical characteristics.Conventionally, refractive index adjusting agents have been added forthe adjustment of the refractive index. Regarding the refractive indexadjusting agents, inorganic oxide particles and the like are used toincrease the refractive index.

Furthermore, it is preferable that transparent resin members containingultraviolet absorbers including optical molded articles are transparentafter molding or after a lapse of time in view of applications, and thusultraviolet absorbers are needed from the viewpoint of preventingdeterioration of optical characteristics caused by opacification ordiscoloration due to ultraviolet-induced degradation. Particularly forglasses lens or contact lenses, ultraviolet absorbers are needed fromthe viewpoint of protecting eyes from ultraviolet ray.

In glasses lens and the like, increase of the refractive index of theresin proceeds, and there are additives, such as an ultravioletabsorber, having refractive indices that are lower than that of theresin. In this case, as the refractive indices of the additives arelower, and the amounts of addition of the additives become larger, theoverall refractive index of the resin is lowered. Therefore, there is aneed for an ultraviolet absorber which has a higher refractive index andcan be added in high concentrations.

CITATION LIST Patent Literature

Patent Literature 1: JP 2012-184168 A

Patent Literature 2: JP 2005-504047 W

Patent Literature 3: JP 2013-67811 A

Patent Literature 4: JP 06-505744 W

SUMMARY OF INVENTION Technical Problem

However, a significant number of conventional organic ultravioletabsorbers have limited compatibility with the resins of matrices, anduniform dissolution of their organic ultraviolet absorbers and resins inhigh concentrations has been difficult. Also, when the organicultraviolet absorbers are added in high concentrations, the resins arecaused cloudiness and impaired transparency. Therefore, in applicationswhere high transparency is required, if it is wished to sufficientlymanifest performances such as ultraviolet absorbency and provision of ahigh refractive index, there have been restrictions on the concentrationof ultraviolet absorbers for the resins. Furthermore, conventionalorganic ultraviolet absorbers have a possibility of being thermallydecomposed when a resin containing an ultraviolet absorber is heated andthen is subjected to molding and processing, and an obtained resinmember may have impaired ultraviolet absorbency, while a transparentresin member may have impaired transparency. Also, there is a risk thatthe molding processing apparatus may be contaminated.

That is, there has been a demand for an additive that has excellent heatresistance, has satisfactory compatibility with a resin that serves as amatrix, can sufficiently exhibit performances such as ultravioletabsorption and increased refractive index while maintaining hightransparency of the resins, and can be dissolved to the resins in highconcentrations.

Furthermore, there are only few studies concerning a technology whichenables imparting of ultraviolet absorbency and a high refractive indexby means of a single additive. For example, in the technologiesspecifically disclosed in Patent Literatures 1 to 3, no investigationwas conducted on sulfur-containing compounds, and a high refractiveindex cannot be imparted. Therefore, in the field of optical materialssuch as optical films, optical sheets, optical plates (plate-likemembers), and other optical molded articles, for example, optical lensessuch as glasses lens or the like, both functions of ultravioletabsorbency and refractive index characteristics are required in manycase. However, in order to satisfy all of such requirements, anultraviolet absorbing layer to which an ultraviolet absorber has beenadded, and a high refractive index layer to which a refractive indexadjusting agent has been added are laminated as separate layers.

Patent Literature 4 discloses a 5-thio-substituted benzotriazoleultraviolet absorber. This ultraviolet absorber which protects organicsubstances against harmful action caused by exposure to ultraviolet rayand suppresses degradation of the organic substances over time providesa stabilized composition. However, investigations focused on heatresistance and high refractive index characteristics of the ultravioletabsorber, suitability to a transparent resin matrix, compatibility(transparency) with a resin serving as a matrix, suppression ofyellowing of a resin matrix, provision of a high refractive index to aresin member containing the ultraviolet absorber, suppression ofdeterioration of the ultraviolet absorbency and external appearance of aresin member caused by thermal decomposition of the ultravioletabsorber, and deterioration of transparency and yellowing in atransparent resin member, have not been achieved in the study.

The present invention was achieved in view of such circumstances asdescribed above, and it is a principal object to provide an additive forimparting ultraviolet absorbency, or an additive for imparting a highrefractive index, which has satisfactory compatibility with a resinserving as a matrix, can maintain high transparency even if added inhigh concentrations, and has excellent heat resistance; and a resinmember using the additive.

It is another object of the present invention to provide an excellentheat resistant additive having the function of imparting bothultraviolet absorbency and a high refractive index can be realized bymeans of one kind of additive while maintaining transparency of matrix;and a resin member using the additive.

Solution to Problem

In order to solve the problems described above, the additive of thepresent invention is an additive for imparting ultraviolet absorbencyand/or a high refractive index to a matrix, the additive having thefollowing features.

[1] An additive for imparting ultraviolet absorbency and/or a highrefractive index to a matrix, the additive being represented by thefollowing Formula (I):

wherein in Formula (I), R^(1a) to R^(9a) each independently represent amonovalent group selected from a monovalent sulfur-containing grouprepresented by the following Formula (i-1) or Formula (i-2), a hydrogenatom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, anaromatic group, an unsaturated group, a sulfur-containing group, anoxygen-containing group, a phosphorus-containing group, an alicyclicgroup, and a halogen atom:

R^(10a)

_(m)SH  (i-1)

R^(11a)

_(n)S

R^(12a)—S

_(p)R^(13a)  (i-2)

wherein in Formula (i-1), R^(10a) represents a divalent hydrocarbongroup having 1 to 12 carbon atoms which may be substituted a hydrogenatom with, interrupted at least any one of two terminals by orinterrupted a carbon-carbon bond by a monovalent or divalent groupselected from an aromatic group, an unsaturated group, asulfur-containing group, an oxygen-containing group, aphosphorus-containing group, an alicyclic group and a halogen atom; andm represents an integer of 0 or 1, and

in Formula (i-2), R^(11a) represents a divalent hydrocarbon group having1 to 20 carbon atoms which may be substituted a hydrogen atom with,interrupted at least any one of two terminals by or interrupted acarbon-carbon bond by a monovalent or divalent group selected from anaromatic group, an unsaturated group, a sulfur-containing group, anoxygen-containing group, a phosphorus-containing group, an alicyclicgroup and a halogen atom; R^(12a) represents, or if p is 2 or larger,R^(12a)'s each independently represent, a divalent hydrocarbon grouphaving 1 to 20 carbon atoms which may be substituted a hydrogen atomwith, interrupted at least any one of two terminals by or interrupted acarbon-carbon bond by a monovalent or divalent group selected from anaromatic group, an unsaturated group, a sulfur-containing group, anoxygen-containing group, a phosphorus-containing group, an alicyclicgroup and a halogen atom; R^(13a) represents a hydrogen atom, or a grouprepresented by —(R^(14a))_(l)—R^(15a) (wherein R^(14a) represents adivalent hydrocarbon group having 1 to 20 carbon atoms which may besubstituted a hydrogen atom with, interrupted a proximal terminal by orinterrupted a carbon-carbon bond by a monovalent or divalent groupselected from an aromatic group, an unsaturated group, asulfur-containing group, an oxygen-containing group, aphosphorus-containing group, an alicyclic group and a halogen atom;R^(15a) represents a hydrogen atom, or a substituent containing any oneskeleton selected from benzotriazole, benzophenone, a benzoic acid esterand triazine; and l represents an integer of 0 or 1); the total numberof carbon atoms of R^(11a), p units of R^(12a), and R^(13a) is 25 orless; n represents an integer of 0 or 1; and p represents an integerfrom 0 to 3,

with the proviso that at least one of R^(1a) to R^(9a) represents amonovalent sulfur-containing group represented by Formula (i-1) orFormula (i-2).

[2] The additive according to [1], wherein the matrix is a transparentresin.

[3] The additive according to [1] or [2], wherein the monovalentsulfur-containing group is a group represented by Formula (i-1), and inthe monovalent sulfur-containing group represented by this Formula(i-1), m is 0, or m is 1, with R^(10a) including an alkylene grouphaving 10 or fewer carbon atoms.

[4] The additive according to [1] or [2], wherein the monovalentsulfur-containing group is a group represented by Formula (i-1), and inthis monovalent sulfur-containing group represented by Formula (i-1), mis 0, or m is 1, with R^(10a) including an alkylene group having 9 orfewer carbon atoms, while the additive has a melting point of 91° C. orlower at normal pressure.

[5] The additive according to [1] or [2], wherein the monovalentsulfur-containing group is a group represented by Formula (i-1), and inthis monovalent sulfur-containing group represented by Formula (i-1), mis 0, or m is 1, with R^(10a) including an alkylene group having 8 orfewer carbon atoms, while the additive has a melting point of below 70°C. at normal pressure.

[6] The additive according to [1] or [2], wherein the monovalentsulfur-containing group is a group represented by Formula (i-1), and inthis monovalent sulfur-containing group represented by Formula (i-1), mis 0, or m is 1, with R^(10a) including an alkylene group having 8 orfewer carbon atoms, while the additive has a melting point of 35° C. orlower at normal pressure.

[7] The additive according to [1] or [2], wherein the monovalentsulfur-containing group is a group represented by Formula (i-1), and inthis monovalent sulfur-containing group represented by Formula (i-1), mis 0, or m is 1, with R^(10a) being an oxyalkylene group having 10 orfewer carbon atoms and having an ether bond at the proximal terminal.

[8] The additive according to [1] or [2], wherein the monovalentsulfur-containing group is a group represented by Formula (i-2), and theadditive has this monovalent sulfur-containing group represented byFormula (i-2) at any of the positions of R^(1a) to R^(5a).

[9] The additive according to [8], wherein in the monovalentsulfur-containing group represented by Formula (i-2), R^(11a) and punits of R^(12a) each include an alkylene group having 18 or fewercarbon atoms, and R^(13a) includes an alkyl group having 18 or fewercarbon atoms.

[10] The additive according to [8], wherein in the monovalentsulfur-containing group represented by Formula (i-2), R^(11a) and punits of R^(12a) each include an alkylene group having 18 or fewercarbon atoms, and R^(13a) includes an alkyl group having 18 or fewercarbon atoms, while the additive has a melting point of 91° C. or lowerat normal pressure.

[11] The additive according to [8], wherein in the monovalentsulfur-containing group represented by Formula (i-2), R^(11a) and punits of R^(12a) each include an alkylene group having 12 or fewercarbon atoms, and R^(13a) includes an alkyl group having 12 or fewercarbon atoms, while the additive has a melting point of 91° C. or lowerat normal pressure.

[12] The additive according to [8], wherein in the monovalentsulfur-containing group represented by Formula (i-2), R^(11a) and punits of R^(12a) each include an alkylene group having 10 or fewercarbon atoms, and R^(13a) includes an alkyl group having 10 or fewercarbon atoms, while the additive has a melting point of 91° C. or lowerat normal pressure.

[13] The additive according to [8], wherein in the monovalentsulfur-containing group represented by Formula (i-2), R^(11a) and punits of R^(12a) each include an alkylene group having 10 or fewercarbon atoms, and R^(13a) includes an alkyl group having 10 or fewercarbon atoms, while the additive has a melting point of below 70° C. atnormal pressure.

[14] The additive according to [8], wherein in the monovalentsulfur-containing group represented by Formula (i-2), R^(11a) and punits of R^(12a) each includes an alkylene group having 8 or fewercarbon atoms, and R^(13a) includes an alkyl group having 8 or fewercarbon atoms, while the additive has a melting point of below 70° C. atnormal pressure.

[15] The additive according to [8], wherein in the monovalentsulfur-containing group represented by Formula (i-2), R^(11a) and punits of R^(12a) each includes an alkylene group having 8 or fewercarbon atoms, and R^(13a) includes an alkyl group having 8 or fewercarbon atoms, while the additive has a melting point of 35° C. or lowerat normal pressure.

[16] The additive according to [1] or [2], wherein the additive has amonovalent sulfur-containing group represented by Formula (i-2) at anyof the positions of R^(6a) to R^(9a).

[17] The additive according to [16], wherein in the monovalentsulfur-containing group represented by Formula (i-2), n is 0, p units ofR^(12a) each include an alkylene group having 18 or fewer carbon atoms,and R^(13a) includes an alkyl group having 18 or fewer carbon atoms.

[18] The additive according to [16], wherein in the monovalentsulfur-containing group represented by Formula (i-2), n is 0, p units ofR^(12a) each includes an alkylene group having 8 or fewer carbon atoms,and R^(13a) includes an alkyl group having 8 or fewer carbon atoms,while the additive has a melting point of below 70° C. at normalpressure.

[19] The additive according to [16], wherein in the monovalentsulfur-containing group represented by Formula (i-2), n and p are each0, and R^(13a) includes an alkyl group having 18 or fewer carbon atoms.

[20] The additive according to [16], wherein in the monovalentsulfur-containing group represented by Formula (i-2), n and p are each0, and R^(13a) includes an alkyl group having 18 or fewer carbon atoms,while the additive has a melting point of 91° C. or lower at normalpressure.

[21] The additive according to [16], wherein in the monovalentsulfur-containing group represented by Formula (i-2), n and p are each0, and R^(13a) includes an alkyl group having 12 or fewer carbon atoms,while the additive has a melting point of 91° C. or lower at normalpressure.

[22] The additive according to [16], wherein in the monovalentsulfur-containing group represented by Formula (i-2), n and p are each0, and R^(13a) includes an alkyl group having 10 or fewer carbon atoms,while the additive has a melting point of 91° C. or lower at normalpressure.

[23] The additive according to [16], wherein in the monovalentsulfur-containing group represented by Formula (i-2), n and p are each0, and R^(13a) includes an alkyl group having 4 to 10 carbon atoms,while the additive has a melting point of 91° C. or lower at normalpressure.

[24] The additive according to [16], wherein in the monovalentsulfur-containing group represented by Formula (i-2), n and p are each0, and R^(13a) includes an alkyl group having 6 to 10 carbon atoms,while the additive has a melting point of below 70° C. at normalpressure.

[25] The additive according to [16], wherein in the monovalentsulfur-containing group represented by Formula (i-2), n and p are each0, and R^(13a) includes an alkyl group having 6 to 10 carbon atoms,while the additive has a melting point of 35° C. or lower at normalpressure.

[26] The additive according to any one of [17] to [25], wherein thesubstituents for R^(1a) to R^(5a) are each selected from a methyl group,a t-butyl group, and a hydroxyl group, and there is one or fewer t-butylgroup.

[27] The additive according to any one of [16] to [26], wherein a lightabsorption peak in a 100 μM chloroform solution of the additive isobserved at 350 to 390 nm, and the absolute value of the slope of astraight line connecting this absorption peak with a peak end of theabsorption spectrum on the longer wavelength side is 0.025 or larger.

[28] The additive according to [27], wherein the additive has amonovalent sulfur-containing group represented by Formula (i-2), at theposition of either R^(7a) or R^(8a).

[29] The additive according to [16], wherein the substituents for R^(1a)to R^(5a) are each selected from a methyl group, a t-butyl group, and ahydroxyl group, and there is one or fewer t-butyl group.

[30] The additive according to [28], wherein the substituents for R^(1a)to R^(5a) are each selected from a methyl group, a t-butyl group, and ahydroxyl group, and there is one or fewer t-butyl group.

[31] An additive for imparting ultraviolet absorbency and/or a highrefractive index to a matrix, the additive being represented by thefollowing Formula (II):

wherein R^(1b) to R^(10b) each independently represent a monovalentgroup selected from a monovalent sulfur-containing group represented bythe following Formula (ii-1) or Formula (ii-2), a hydrogen atom, amonovalent hydrocarbon group having 1 to 10 carbon atoms, an aromaticgroup, an unsaturated group, a sulfur-containing group, anoxygen-containing group, a phosphorus-containing group, an alicyclicgroup, and a halogen atom:

R^(11b)

_(q)SH  (ii-1)

R^(12b)

_(r)S

R^(13b)—S

_(s)R^(14b)  (ii-2)

wherein in Formula (ii-1), R^(11b) represents a divalent hydrocarbongroup having 1 to 12 carbon atoms which may be substituted a hydrogenatom with, interrupted at least any one of two terminals by orinterrupted a carbon-carbon bond by a monovalent or divalent groupselected from an aromatic group, an unsaturated group, asulfur-containing group, an oxygen-containing group, aphosphorus-containing group, an alicyclic group and a halogen atom; andq represents an integer of 0 or 1, and

in Formula (ii-2), R^(12b) represents a divalent hydrocarbon grouphaving 1 to 20 carbon atoms which may be substituted a hydrogen atomwith, interrupted at least any one of two terminals by or interrupted acarbon-carbon bond by a monovalent or divalent group selected from anaromatic group, an unsaturated group, a sulfur-containing group, anoxygen-containing group, a phosphorus-containing group, an alicyclicgroup and a halogen atom; R^(13b) represents, or if s is 2 or larger,R^(13b)'s each independently represent, a divalent hydrocarbon grouphaving 1 to 20 carbon atoms which may be substituted a hydrogen atomwith, interrupted at least any one of two terminals by or interrupted acarbon-carbon bond by a monovalent or divalent group selected from anaromatic group, an unsaturated group, a sulfur-containing group, anoxygen-containing group, a phosphorus-containing group, an alicyclicgroup and a halogen atom; R^(14b) represents a monovalent hydrocarbongroup having 1 to 20 carbon atoms which may be substituted a hydrogenatom with, interrupted a proximal terminal by or interrupted acarbon-carbon bond by a monovalent or divalent group selected from anaromatic group, an unsaturated group, a sulfur-containing group, anoxygen-containing group, a phosphorus-containing group, an alicyclicgroup and a halogen atom; the total number of carbon atoms of R^(12b), sunits of R^(13b) and R^(14b) is 25 or less; r represents an integer of 0or 1; and s represents an integer from 0 to 3,

with the proviso that at least one of R^(1b) to R^(10b) is a monovalentsulfur-containing group represented by Formula (ii-1) or Formula (ii-2).

[32] The additive according to [31], wherein the matrix is a transparentresin.

[33] The additive according to [31] or [32], wherein the monovalentsulfur-containing group is a group represented by Formula (ii-1), and inthis monovalent sulfur-containing group represented by Formula (ii-1), qis 0, or q is 1, with R^(11b) including an alkylene group having 10 orfewer carbon atoms.

[34] The additive according to [31] or [32], wherein the monovalentsulfur-containing group is a group represented by Formula (ii-1), and inthis monovalent sulfur-containing group represented by Formula (ii-1), qis 0, or q is 1, with R^(11b) including an alkylene group having 9 orfewer carbon atoms, while the additive has a melting point of 91° C. orlower at normal pressure.

[35] The additive according to [31] or [32], wherein the monovalentsulfur-containing group is a group represented by Formula (ii-1), and inthis monovalent sulfur-containing group represented by Formula (ii-1), qis 0, or q is 1, with R^(11b) including an alkylene group having 8 orfewer carbon atoms, while the additive has a melting point of below 70°C. at normal pressure.

[36] The additive according to [31] or [32], wherein the monovalentsulfur-containing group is a group represented by Formula (ii-1), and inthis monovalent sulfur-containing group represented by Formula (ii-1), qis 0, or q is 1, with R^(11b) including an alkylene group having 8 orfewer carbon atoms, while the additive has a melting point of 35° C. orlower at normal pressure.

[37] The additive according to [31] or [32], wherein the monovalentsulfur-containing group is a group represented by Formula (ii-1), and inthis monovalent sulfur-containing group represented by Formula (ii-1), qis 0, or q is 1, with R^(11b) being an oxyalkylene group having 10 orfewer carbon atoms and having an ether bond at the proximal terminal.

[38] The additive according to [31] or [32], wherein the monovalentsulfur-containing group is a group represented by Formula (ii-2), and inthis monovalent sulfur-containing group represented by Formula (ii-2),R^(12b) and s units of R^(13b) each includes an alkylene group having 18or fewer carbon atoms, while R^(14b) includes an alkyl group having 18or fewer carbon atoms.

[39] The additive according to [31] or [32], wherein the monovalentsulfur-containing group is a group represented by Formula (ii-2), and inthis monovalent sulfur-containing group represented by Formula (ii-2),R^(12b) and s units of R^(13b) each includes an alkylene group having 18or fewer carbon atoms, and R^(14b) includes an alkyl group having 18 orfewer carbon atoms, while the additive has a melting point of 91° C. orlower at normal pressure.

[40] The additive according to [31] or [32], wherein the monovalentsulfur-containing group is a group represented by Formula (ii-2), and inthis monovalent sulfur-containing group represented by Formula (ii-2),R^(12b) and s units of R^(13b) each includes an alkylene group having 12or fewer carbon atoms, and R^(14b) includes an alkyl group having 12 orfewer carbon atoms, while the additive has a melting point of 91° C. orlower at normal pressure.

[41] The additive according to [31] or [32], wherein the monovalentsulfur-containing group is a group represented by Formula (ii-2), and inthis monovalent sulfur-containing group represented by Formula (ii-2),R^(12b) and s units of R^(13b) each includes an alkylene group having 10or fewer carbon atoms, and R^(14b) includes an alkyl group having 10 orfewer carbon atoms, while the additive has a melting point of 91° C. orlower at normal pressure.

[42] The additive according to [31] or [32], wherein the monovalentsulfur-containing group is a group represented by Formula (ii-2), and inthis monovalent sulfur-containing group represented by Formula (ii-2),R^(12b) and s units of R^(13b) each includes an alkylene group having 10or fewer carbon atoms, and R^(14b) includes an alkyl group having 10 orfewer carbon atoms, while the additive has a melting point of below 70°C. at normal pressure.

[43] The additive according to [31] or [32], wherein the monovalentsulfur-containing group is a group represented by Formula (ii-2), and inthis monovalent sulfur-containing group represented by Formula (ii-2),R^(12b) and s units of R^(13b) each includes an alkylene group having 8or fewer carbon atoms, and R^(14b) includes an alkyl group having 8 orfewer carbon atoms, while the additive has a melting point of below 70°C. at normal pressure.

[44] The additive according to [31] or [32], wherein the monovalentsulfur-containing group is a group represented by Formula (ii-2), and inthis monovalent sulfur-containing group represented by Formula (ii-2),R^(12b) and s units of R^(13b) each includes an alkylene group having 8or fewer carbon atoms, and R^(14b) includes an alkyl group having 8 orfewer carbon atoms, while the additive has a melting point of 35° C. orlower at normal pressure.

[45] An additive for imparting ultraviolet absorbency and/or a highrefractive index to a matrix, the additive being represented by thefollowing Formula (III):

wherein R^(1c) to R^(10c) each independently represent a monovalentgroup selected from a monovalent sulfur-containing group represented bythe following Formula (iii-1) or Formula (iii-2), a hydrogen atom, amonovalent hydrocarbon group having 1 to 10 carbon atoms, an aromaticgroup, an unsaturated group, a sulfur-containing group, anoxygen-containing group, a phosphorus-containing group, an alicyclicgroup, and a halogen atom:

R^(11c)

_(t)SH  (iii-1)

R^(12c)

_(u)S

R^(13c)—S

_(v)R^(14c)  (iii-2)

wherein in Formula (iii-1), R^(11c) represents a divalent hydrocarbongroup having 1 to 12 carbon atoms which may be substituted a hydrogenatom with, interrupted at least any one of two terminals by orinterrupted a carbon-carbon bond by a monovalent or divalent groupselected from an aromatic group, an unsaturated group, asulfur-containing group, an oxygen-containing group, aphosphorus-containing group, an alicyclic group and a halogen atom; andt represents an integer of 0 or 1, and

in Formula (iii-2), R^(12c) represents a divalent hydrocarbon grouphaving 1 to 20 carbon atoms which may be substituted a hydrogen atomwith, interrupted at least any one of two terminals by or interrupted acarbon-carbon bond by a monovalent or divalent group selected from anaromatic group, an unsaturated group, a sulfur-containing group, anoxygen-containing group, a phosphorus-containing group, an alicyclicgroup and a halogen atom; R^(13c) represents, or if v is 2 or larger,R^(13c)'s each independently represent, a divalent hydrocarbon grouphaving 1 to 20 carbon atoms which may be substituted a hydrogen atomwith, interrupted at least any one of two terminals by or interrupted acarbon-carbon bond by a monovalent or divalent group selected from anaromatic group, an unsaturated group, a sulfur-containing group, anoxygen-containing group, a phosphorus-containing group, an alicyclicgroup and a halogen atom; R^(14c) represents a monovalent hydrocarbongroup having 1 to 20 carbon atoms which may be substituted a hydrogenatom with, interrupted a proximal terminal by or interrupted acarbon-carbon bond by a monovalent or divalent group selected from anaromatic group, an unsaturated group, a sulfur-containing group, anoxygen-containing group, a phosphorus-containing group, an alicyclicgroup and a halogen atom; the total number of carbon atoms of R^(12c), vunits of R^(13c) and R^(14c) is 25 or less; u represents an integer of 0or 1; and v represents an integer from 0 to 3,

with the proviso that at least one of R^(1c) to R^(10c) is a monovalentsulfur-containing group represented by Formula (iii-1) or Formula(iii-2).

[46] The additive according to [45], wherein the matrix is a transparentresin.

[47] The additive according to [43] or [44], wherein the monovalentsulfur-containing group is a group represented by Formula (iii-1), andin this monovalent sulfur-containing group represented by Formula(iii-1), t is 0, or t is 1, with R^(11c) including an alkylene grouphaving 10 or fewer carbon atoms.

[48] The additive according to [45] or [46], wherein the monovalentsulfur-containing group is a group represented by Formula (iii-1), andin this monovalent sulfur-containing group represented by Formula(iii-1), t is 0, or t is 1, with R^(11c) including an alkylene grouphaving 9 or fewer carbon atoms, while the additive has a melting pointof 91° C. or lower at normal pressure.

[49] The additive according to [45] or [46], wherein the monovalentsulfur-containing group is a group represented by Formula (iii-1), andin this monovalent sulfur-containing group represented by Formula(iii-1), t is 0, or t is 1, with R^(11c) including an alkylene grouphaving 8 or fewer carbon atoms, while the additive has a melting pointof below 70° C. at normal pressure.

[50] The additive according to [45] or [46], wherein the monovalentsulfur-containing group is a group represented by Formula (iii-1), andin this monovalent sulfur-containing group represented by Formula(iii-1), t is 0, or t is 1, with R^(11c) including an alkylene grouphaving 8 or fewer carbon atoms, while the additive has a melting pointof 35° C. or lower at normal pressure.

[51] The additive according to [45] or [46], wherein the monovalentsulfur-containing group is a group represented by Formula (iii-1), andin this monovalent sulfur-containing group represented by Formula(iii-1), t is 0, or t is 1, with R^(11c) being an oxyalkylene grouphaving 10 or fewer carbon atoms and having an ether bond at the proximalterminal.

[52] The additive according to [45] or [46], wherein the monovalentsulfur-containing group is a group represented by Formula (iii-2), andin this monovalent sulfur-containing group represented by Formula(iii-2), R^(12c) and v units of R^(13c) each includes an alkylene grouphaving 18 or fewer carbon atoms, while R^(14c) includes an alkyl grouphaving 18 or fewer carbon atoms.

[53] The additive according to [45] or [46], wherein the monovalentsulfur-containing group is a group represented by Formula (iii-2), andin this monovalent sulfur-containing group represented by Formula(iii-2), R^(12c) and v units of R^(13c) each includes an alkylene grouphaving 18 or fewer carbon atoms, and R^(14c) includes an alkyl grouphaving 18 or fewer carbon atoms, while the additive has a melting pointof 91° C. or lower at normal pressure.

[54] The additive according to [45] or [46], wherein the monovalentsulfur-containing group is a group represented by Formula (iii-2), andin this monovalent sulfur-containing group represented by Formula(iii-2), R^(12c) and v units of R^(13c) each includes an alkylene grouphaving 12 or fewer carbon atoms, and R^(14c) includes an alkyl grouphaving 12 or fewer carbon atoms, while the additive has a melting pointof 91° C. or lower at normal pressure.

[55] The additive according to [45] or [46], wherein the monovalentsulfur-containing group is a group represented by Formula (iii-2), andin this monovalent sulfur-containing group represented by Formula(iii-2), R^(12c) and v units of R^(13c) each includes an alkylene grouphaving 10 or fewer carbon atoms, and R^(14c) includes an alkyl grouphaving 10 or fewer carbon atoms, while the additive has a melting pointof 91° C. or lower at normal pressure.

[56] The additive according to [45] or [46], wherein the monovalentsulfur-containing group is a group represented by Formula (iii-2), andin this monovalent sulfur-containing group represented by Formula(iii-2), R^(12c) and v units of R^(13c) each includes an alkylene grouphaving 10 or fewer carbon atoms, and R^(14c) includes an alkyl grouphaving 10 or fewer carbon atoms, while the additive has a melting pointof below 70° C. at normal pressure.

[57] The additive according to [45] or [46], wherein the monovalentsulfur-containing group is a group represented by Formula (iii-2), andin this monovalent sulfur-containing group represented by Formula(iii-2), R^(12c) and v units of R^(13c) each includes an alkylene grouphaving 8 or fewer carbon atoms, and R^(14c) includes an alkyl grouphaving 8 or fewer carbon atoms, while the additive has a melting pointof below 70° C. at normal pressure.

[58] The additive according to [45] or [46], wherein the monovalentsulfur-containing group is a group represented by Formula (iii-2), andin this monovalent sulfur-containing group represented by Formula(iii-2), R^(12c) and v units of R^(13c) each includes an alkylene grouphaving 8 or fewer carbon atoms, and R^(14c) includes an alkyl grouphaving 8 or fewer carbon atoms, while the additive has a melting pointof 35° C. or lower at normal pressure.

[59] An additive for imparting ultraviolet absorbency and/or a highrefractive index to a matrix, the additive being represented by thefollowing Formula (IV):

wherein R^(1d) to R^(15d) each independently represent a monovalentgroup selected from a monovalent sulfur-containing group represented bythe following Formula (iv-1) or Formula (iv-2), a hydrogen atom, amonovalent hydrocarbon group having 1 to 10 carbon atoms, an aromaticgroup, an unsaturated group, a sulfur-containing group, anoxygen-containing group, a phosphorus-containing group, an alicyclicgroup, and a halogen atom:

R^(16d)

_(w)SH  (iv-1)

R^(17d)

_(x)S

R^(18d)—S

_(y)R^(19d)  (iv-2)

wherein in Formula (iv-1), R^(16d) represents a divalent hydrocarbongroup having 1 to 12 carbon atoms which may be substituted a hydrogenatom with, interrupted at least any one of two terminals by orinterrupted a carbon-carbon bond by a monovalent or divalent groupselected from an aromatic group, an unsaturated group, asulfur-containing group, an oxygen-containing group, aphosphorus-containing group, an alicyclic group and a halogen atom; andw represents an integer of 0 or 1, and

in Formula (iv-2), R^(17d) represents a divalent hydrocarbon grouphaving 1 to 20 carbon atoms which may be substituted a hydrogen atomwith, interrupted at least any one of two terminals by or interrupted acarbon-carbon bond by a monovalent or divalent group selected from anaromatic group, an unsaturated group, a sulfur-containing group, anoxygen-containing group, a phosphorus-containing group, an alicyclicgroup and a halogen atom; R^(18d) represents, or if y is 2 or larger,R^(18d)'s each independently represent, a divalent hydrocarbon grouphaving 1 to 20 carbon atoms which may be substituted a hydrogen atomwith, interrupted at least any one of two terminals by or interrupted acarbon-carbon bond by a monovalent or divalent group selected from anaromatic group, an unsaturated group, a sulfur-containing group, anoxygen-containing group, a phosphorus-containing group, an alicyclicgroup and a halogen atom; R^(19d) represents a monovalent hydrocarbongroup having 1 to 20 carbon atoms which may be substituted a hydrogenatom with, interrupted a proximal terminal by or interrupted acarbon-carbon bond by a monovalent or divalent group selected from anaromatic group, an unsaturated group, a sulfur-containing group, anoxygen-containing group, a phosphorus-containing group, an alicyclicgroup and a halogen atom; the total number of carbon atoms of R^(17d), yunits of R^(18d) and R^(19d) is 25 or less; x represents an integer of 0or 1; and y represents an integer from 0 to 3,

with the proviso that at least one of R^(1d) to R^(15d) is a monovalentsulfur-containing group represented by Formula (iv-1) or Formula (iv-2).

[60] The additive according to [59], wherein the matrix is a transparentresin.

[61] The additive according to [59] or [60], wherein the monovalentsulfur-containing group is a group represented by Formula (iv-1) orFormula (iv-2), and in this monovalent sulfur-containing grouprepresented by Formula (iv-1), w is 0, or w is 1, with R^(16d) includingan alkylene group having 8 or fewer carbon atoms, while in themonovalent sulfur-containing group represented by Formula (iv-2),R^(17d) and y units of R^(18d) each includes an alkylene group having 8or fewer carbon atoms, with R^(19d) including an alkyl group having 8 orfewer carbon atoms.

[62] An additive for imparting ultraviolet absorbency and/or a highrefractive index to a matrix, the additive being represented by thefollowing Formula (V):

wherein R^(1e) to R^(9e) each independently represent a monovalent groupselected from an alkyl group having 10 to 24 carbon atoms and having astraight chain having 10 to 20 carbon atoms, with the straight chainoptionally being substituted with two or fewer alkyl groups each having1 or 2 carbon atoms, a hydrogen atom, a monovalent hydrocarbon grouphaving 1 to 4 carbon atoms, an aromatic group, an unsaturated group, anoxygen-containing group, a phosphorus-containing group, an alicyclicgroup, and a halogen atom; and at least one of R^(1e) to R^(9e) is thealkyl group having 10 to 24 carbon atoms.

[63] The additive according to [62], wherein the matrix is a transparentresin.

[64] The additive of the present invention is such that in regard to theadditive according to any one of [1] to [64], a reactive functionalgroup is bonded to at least any one group selected from R^(1a) toR^(13a), R^(1b) to R^(14b), R^(1c) to R^(14c), and R^(1d) to R^(19d) ofFormulae (I) to (IV).

[65] The resin member of the present invention includes the additiveaccording to any one of [1] to [15] and [31] to [64] in the resin of thematrix.

[66] The transparent resin member of the present invention includes theadditive according to any one of [1] to [15] and [31] to [64] in theresin of the matrix.

[67] The resin member of the present invention includes the additiveaccording to any one of [16] to [30] in the resin of the matrix.

[68] The transparent resin member of the present invention includes theadditive according to any one of [16] to [30] in the resin of thematrix.

[69] The resin member of the present invention is such that the resinmember according to any one of [65] to [68] is one layer in a memberhaving a laminated multilayer structure, a film, a sheet, a plate-likemember, or an optical resin.

Advantageous Effects of Invention

When the additive of the present invention is used, the additive hassatisfactory compatibility with the resin as a matrix, has excellentheat resistance, and can maintain high transparency even if added in lowconcentrations to high concentrations. Accordingly, the performance ofimparting ultraviolet absorbency or a high refractive index can besufficiently manifested through addition in high concentrations, whiletransparency is maintained.

Furthermore, when the additive of the present invention is used, thefunction of imparting both ultraviolet absorbency and a high refractiveindex can be manifested by means of a single kind of additive.

A resin member containing the additive of the present invention exhibitstransparency even under the conditions in which the concentration of theadditive widely ranges from low concentrations to high concentrations,due to the heat resistance and compatibility with resins of theadditive, and the resin member is imparted with a high refractive indexand/or ultraviolet absorbency. Particularly, under the conditions ofhigh concentrations, transparency is maintained, and a higher refractiveindex and/or higher ultraviolet absorbency can be imparted. Furthermore,a laminated multilayer structure is simplified, and reduction in thenumber of production processes and production cost is enabled.Furthermore, the resin member can be applied to higher resin moldingprocessing temperatures.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 shows ultraviolet-visible light absorption spectra (UV charts) ofExamples 36 to 40 (benzotriazole-based).

FIG. 2 shows ultraviolet-visible light absorption spectra (UV charts) ofExamples 41 to 44 and Comparative Example 9 (benzotriazole-based).

FIG. 3 shows ultraviolet-visible light absorption spectra (UV charts) ofExamples 45 to 49 (benzotriazole-based).

FIG. 4 shows ultraviolet-visible light absorption spectra (UV charts) ofExamples 50 to 54 (benzotriazole-based).

FIGS. 5A and 5B show ultraviolet-visible light absorption spectra (UVcharts) of Examples 55 to 60 and Comparative Example 10(benzotriazole-based).

FIG. 6 shows ultraviolet-visible light absorption spectra (UV charts) ofExamples 61 to 64 and Comparative Example 11 (benzophenone-based).

FIG. 7 shows ultraviolet-visible light absorption spectra (UV charts) ofExamples 65 and 66 and Comparative Example 12 (salicylate-based).

FIG. 8 shows ultraviolet-visible light absorption spectra (UV charts) ofExamples 67 to 70 and Comparative Example 13 (triazine-based).

FIG. 9 is a graph obtained by measuring the absorption peaks of Compound21 at the concentrations of 10, 25 and 50 μM, and plotting the absolutevalue of the slope on the longer wavelength side of the absorption peakin the wavelength region of 350 to 390 nm against the concentration ofthe ultraviolet absorber.

FIG. 10 shows transmission spectra of plastic lenses of Example 71 andComparative Example 14.

FIG. 11 shows transmission spectra of plastic lenses of Example 72 andComparative Example 15.

FIG. 12 shows transmission spectra of plastic lenses of Example 73 andComparative Example 16.

FIG. 13 shows transmission spectra of plastic lenses of Example 74 andComparative Example 17.

FIG. 14 shows transmission spectra of plastic lenses of Example 75 andComparative Example 18.

FIG. 15 shows transmission spectra of plastic lenses of Example 76 andComparative Example 14.

FIG. 16 shows transmission spectra of plastic lenses of Example 77 andComparative Example 14.

FIG. 17 shows photographs of films of Example 10 and Example 13.

DESCRIPTION OF EMBODIMENTS

Hereinafter, the present invention will be explained in detail.

The additives represented by Formula (I) to Formula (IV) described abovehave a feature that sulfur-containing groups have been introduced intobenzotriazole-based, benzophenone-based, salicylate-based, andtriazine-based ultraviolet-absorbing skeletons. Owing to thisintroduction of sulfur-containing groups, compatibility with a resinserving as a matrix is improved, and high transparency can be maintainedeven if added in high concentrations. Furthermore, the weight reductiontemperature increases, and heat resistance is also enhanced. Inaddition, the additives exhibit ultraviolet absorbency due to theultraviolet-absorbing skeletons, and may also exhibit performance ashigh refractive index-imparting agents depending on thesulfur-containing group.

[Substituents]

According to the present invention, examples of the “monovalent ordivalent group selected from an aromatic group, an unsaturated group, asulfur-containing group, an oxygen-containing group, aphosphorus-containing group, an alicyclic group, and a halogen atom”include a group capable of imparting a high refractive index, a groupcapable of adjusting heat resistance and compatibility with a resin, anda group capable of reacting with a resin and/or a monomer of a resin.For example, the following groups are included.

(Aromatic Group)

An aromatic group contains an aromatic ring such as a benzene ring, anaphthalene ring, or an anthracene ring, and the number of carbon atomsis preferably 6 to 18, and more preferably 6 to 14. Examples of amonovalent or divalent aromatic group include a phenyl group, a2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a2,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a3,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a2,4,5-trimethylphenyl group, a 2,4,6-trimethylphenyl group, a 4-biphenylgroup, a 1-naphthyl group, a 2-methoxyphenyl group, a 3-methoxyphenylgroup, a 4-methoxyphenyl group, a 2-ethoxyphenyl group, a 3-ethoxyphenylgroup, a 4-ethoxyphenyl group, a 2-chlorophenyl group, a 2-fluorophenylgroup, a 4-fluorophenyl group, a 2-trifluoromethylphenyl group, a4-trifluoromethylphenyl group, a 1-naphthyl group, and a 2-naphthylgroup.

(Unsaturated Group)

An unsaturated group contains a carbon-carbon or carbon-heteroatomunsaturated bond such as a carbon-carbon double bond, a carbon-carbontriple bond, a carbon-oxygen double bond (a carbonyl group, an aldehydegroup, a carboxyl group, or the like), a carbon-nitrogen double bond (anisocyanate group or the like), or a carbon-nitrogen triple bond (a cyanogroup, a cyanate group or the like), and the number of carbon atoms ispreferably 1 to 10, and more preferably 1 to 8. Examples of themonovalent or divalent unsaturated group include an acryloyl group, amethacryloyl group, a maleic acid monoester group, a styryl group, anallyl group, a vinyl group, an amide group, a carbamoyl group, a cyanogroup, and an isocyanate group.

(Sulfur-Containing Group)

A sulfur-containing group contains a thiol group, a sulfide group, adisulfide group, a sulfonyl group, a sulfo group, a thiocarbonyl group,a thiocarbamoyl group, or a thiourea group, and the number of carbonatoms is preferably 0 to 10. Examples of the monovalent or divalentsulfur-containing group include a thiomethoxy group, a thioethoxy group,a thio-n-propoxy group, a thioisopropoxy group, a thio-n-butoxy group, athio-t-butoxy group, a thiophenoxy group, a p-methylthiophenoxy group, ap-methoxythiophenoxy group, a thiophene group, a thiazole group, a thiolgroup, a sulfo group, a sulfide group, a disulfide group, a sulfonylgroup, a thiocarbonyl group, and a thiourea group.

(Oxygen-Containing Group)

In regard to the oxygen-containing group, in a case in which theoxygen-containing group contains an aromatic ring group or an alicyclicgroup, the number of carbon atoms is preferably 6 to 12; and in a casein which the oxygen-containing group does not contain an aromatic ringgroup or an alicyclic group, the number of carbon atoms is preferably 0to 6. Examples of a monovalent or divalent oxygen-containing groupinclude a hydroxyl group, a methoxy group, an ethoxy group, a propoxygroup, a butoxy group, a phenoxy group, a methylphenoxy group, adimethylphenoxy group, a naphthoxy group, a phenylmethoxy group, aphenylethoxy group, an acetoxy group, an acetyl group, an aldehydegroup, a carboxyl group, a carbamoyl group, a urea group, an ethergroup, a carbonyl group, an ester group, an oxazole group, and amorpholine group.

(Phosphorus-Containing Group)

A phosphorus-containing group contains a phosphine group, a phosphitegroup, a phosphonic acid group, a phosphinic acid group, a phosphoricacid group, or a phosphoric acid ester group. In a case in which thephosphorus-containing group includes an aromatic ring group or analicyclic group, the number of carbon atoms is preferably 6 to 22, andin a case in which the phosphorus-containing group does not include anaromatic ring group or an alicyclic group, the number of carbon atoms ispreferably 0 to 6. Examples of a monovalent or divalentphosphorus-containing group include a trimethylphosphine group, atributylphosphine group, a tricyclohexylphosphine group, atriphenylphosphine group, a tritolylphosphine group, a methylphosphitegroup, an ethylphosphite group, a phenylphosphite group, a phosphonicacid group, a phosphinic acid group, a phosphoric acid group, and aphosphoric acid ester group.

(Alicyclic Group)

In regard to an alicyclic group, the number of carbon atoms ispreferably 3 to 10, and more preferably 3 to 8. Examples of a monovalentor divalent alicyclic group include a cyclopropyl group, a cyclobutylgroup, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, anda cyclooctyl group.

(Halogen Atom)

Examples of the halogen atom include a fluorine atom, a chlorine atom, abromine atom, and an iodine atom.

The additive represented by Formula (V) described above has a featurethat a long-chain alkyl group has been introduced into abenzotriazole-based ultraviolet-absorbing skeleton. Owing to thisintroduction of a long-chain alkyl group, the additive becomes a liquid,acquires satisfactory compatibility with a resin serving as a matrix,and can maintain high transparency even if added in high concentrations.Therefore, a resin member having high transparency and also having highultraviolet absorbency is obtained.

1. Additive Represented by Formula (I)

An additive represented by Formula (I) described above contains theabove-described monovalent sulfur-containing group represented byFormula (i-1) or Formula (i-2) in a benzotriazole-based skeleton.

In Formula (i-1), R^(10a) represents a divalent hydrocarbon group having1 to 12 carbon atoms which may be substituted a hydrogen atom with,interrupted at least any one of two terminals by or interrupted acarbon-carbon bond by a monovalent or divalent group selected from anaromatic group, an unsaturated group, a sulfur-containing group, anoxygen-containing group, a phosphorus-containing group, an alicyclicgroup and a halogen atom.

Examples of the divalent hydrocarbon group of R^(10a) include a linearor branched alkylene group, alkenylene group, and an alkynylene group.Specific examples include a methylene group, an ethane-1,2-diyl group, apropane-1,3-diyl group, a 1-methylethane-1,2-diyl group, abutane-1,4-diyl group, a butane-1,3-diyl group, a2-methylpropane-1,3-diyl group, a pentane-1,5-diyl group, apentane-1,4-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diylgroup, an octane-1,8-diyl group, a nonane-1,9-diyl group, adecane-1,10-diyl group, an undecane-1,11-diyl group, and adodecane-1,12-diyl group.

In a case in which the divalent hydrocarbon group is substituted ahydrogen atom with, interrupted at least any one of two terminals by orinterrupted a carbon-carbon bond by the monovalent or divalent group,the number of the monovalent or divalent groups is preferably 2 or less,and more preferably 1 or less.

Specific examples of the aromatic group, unsaturated group,sulfur-containing group, oxygen-containing group, phosphorus-containinggroup, alicyclic group and halogen atom of the monovalent or divalentgroup include the groups listed as examples in the section[Substituents] described above.

In Formula (i-1), m represents an integer of 0 or 1.

In Formula (i-2), R^(11a) represents a divalent hydrocarbon group having1 to 20 carbon atoms which may be substituted a hydrogen atom with,interrupted at least any one of two terminals by or interrupted acarbon-carbon bond by a monovalent or divalent group selected from anaromatic group, an unsaturated group, a sulfur-containing group, anoxygen-containing group, a phosphorus-containing group, an alicyclicgroup and a halogen atom.

Examples of the divalent hydrocarbon group of R^(11a) include a linearor branched alkylene group, a linear or branched alkenylene group, and alinear or branched alkynylene group. Specific examples include amethylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, a1-methylethane-1,2-diyl group, a butane-1,4-diyl group, abutane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, apentane-1,5-diyl group, a pentane-1,4-diyl group, a hexane-1,6-diylgroup, a heptane-1,7-diyl group, an octane-1,8-diyl group, anonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diylgroup, a dodecane-1,12-diyl group, a tridecan-1,13-yl group, atetradecan-1,14-yl group, a pentadecan-1,15-yl group, ahexadecan-1,16-yl group, a heptadecan-1,17-yl group, anoctadecan-1,18-yl group, a nonadecan-1,19-yl group, and aneicosan-1,20-yl group. Among these, an alkylene group is preferred, anda linear alkylene group is more preferred.

In a case in which the divalent hydrocarbon group of R^(11a) issubstituted a hydrogen atom with, interrupted at least any one of twoterminals by or interrupted a carbon-carbon bond by the monovalent ordivalent group, the number of the monovalent or divalent groups ispreferably 2 or less, and more preferably 1 or less.

Specific examples of the aromatic group, unsaturated group,sulfur-containing group, oxygen-containing group phosphorus-containinggroup, alicyclic group and halogen atom of the monovalent or divalentgroup include the groups listed as examples in the section[Substituents] described above.

In Formula (i-2), in a case in which p is 2 or larger, R^(12a)'s eachindependently represent a divalent hydrocarbon group having 1 to 20carbon atoms which may be substituted a hydrogen atom with, interruptedat least any one of two terminals by or interrupted a carbon-carbon bondby a monovalent or divalent group selected from an aromatic group, anunsaturated group, a sulfur-containing group, an oxygen-containinggroup, a phosphorus-containing group, an alicyclic group and a halogenatom.

Examples of the divalent hydrocarbon group of R^(12a) include thedivalent hydrocarbon groups listed above as examples of the divalenthydrocarbon groups of R^(11a). Among these, an alkylene group ispreferred, and a linear alkylene group is more preferred.

In a case in which the divalent hydrocarbon group of R^(12a) issubstituted a hydrogen atom with, interrupted at least any one of twoterminals by or interrupted a carbon-carbon bond by the monovalent ordivalent group, the number of the monovalent or divalent groups ispreferably 2 or less, and more preferably 1 or less.

Specific examples of the aromatic group, unsaturated group,sulfur-containing group, oxygen-containing group, phosphorus-containinggroup, alicyclic group, and halogen atom of the monovalent or divalentgroup include the groups listed as examples in the section[Substituents] described above.

In Formula (i-2), R^(13a) represents a hydrogen atom, or represents agroup represented by —(R^(14a))_(l)—R^(15a) (wherein R^(14a) representsa divalent hydrocarbon group having 1 to 20 carbon atoms which may besubstituted a hydrogen atom with, interrupted a proximal terminal by orinterrupted a carbon-carbon bond by a monovalent or divalent groupselected from an aromatic group, an unsaturated group, asulfur-containing group, an oxygen-containing group, aphosphorus-containing group, an alicyclic group and a halogen atom;R^(15a) represents a hydrogen atom, or represents a substituentcontaining any one skeleton selected from benzotriazole, benzophenone, abenzoic acid ester, and triazine; and l represents an integer of 0 or1).

Examples of the divalent hydrocarbon group of R^(14a) include thedivalent hydrocarbon groups listed above as examples of the divalenthydrocarbon groups of R^(10a). Among these, an alkylene group ispreferred, and a linear alkylene group is more preferred.

In a case in which the divalent group of R^(14a) is substituted ahydrogen atom with, interrupted a proximal terminal by or interrupted acarbon-carbon bond by the monovalent or divalent group, the number ofthe monovalent or divalent groups is preferably 2 or less, and morepreferably 1 or less.

Specific examples of the aromatic group, unsaturated group,sulfur-containing group, oxygen-containing group, phosphorus-containinggroup, alicyclic group and halogen atom of the monovalent or divalentgroup include the groups listed as examples in the section[Substituents] described above.

In a case in which R^(15a) is a substituent containing any one skeletonselected from benzotriazole, benzophenone, a benzoic acid ester andtriazine, an example of the substituent containing benzotriazole may bea group represented by the following Formula (A), and an example of thesubstituent containing benzophenone may be a group represented by thefollowing Formula (B). An example of the substituent containing abenzoic acid ester may be a group represented by the following Formula(C), and an example of the substituent containing triazine may be agroup represented by the following Formula (D).

In Formula (A), any one among R^(16a) to R^(24a) represents a monovalentbonding moiety that is bonded to R^(14a) or a terminal sulfur atom ofFormula (i-2); and the others of R^(16a) to R^(24a) each independentlyrepresent a monovalent group selected from a hydrogen atom, ahydrocarbon group having 1 to 10 carbon atoms, an aromatic group, anunsaturated group, a sulfur-containing group, an oxygen-containinggroup, a phosphorus-containing group, an alicyclic group and a halogenatom.

In Formula (B), any one among R^(15b) to R^(24b) represents a monovalentbonding moiety that is bonded to R^(14a) or a terminal sulfur atom ofFormula (i-2); and the others of R^(15b) to R^(24b) each independentlyrepresent a monovalent group selected from a hydrogen atom, ahydrocarbon group having 1 to 10 carbon atoms, an aromatic group, anunsaturated group, a sulfur-containing group, an oxygen-containinggroup, a phosphorus-containing group, an alicyclic group and a halogenatom.

In Formula (C), any one among R^(15c) to R^(24c) represents a monovalentbonding moiety that is bonded to R^(14a) or a terminal sulfur atom ofFormula (i-2); and the others of R^(15c) to R^(24c) each independentlyrepresent a monovalent group selected from a hydrogen atom, ahydrocarbon group having 1 to 10 carbon atoms, an aromatic group, anunsaturated group, a sulfur-containing group, an oxygen-containinggroup, a phosphorus-containing group, an alicyclic group, and a halogenatom.

In Formula (D), R^(20d) to R^(22d) each represents any one of thefollowing [a] and [b].

[a] At least one of R^(20d) to R^(22d) represents a monovalent bondingmoiety that is bonded to R^(14a) or a terminal sulfur atom of Formula(i-2), and the others of R^(20d) to R^(22d) each independently representa hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, anaromatic group, an unsaturated group, a sulfur-containing group, anoxygen-containing group, a phosphorus-containing group, an alicyclicgroup, a halogen atom, and a group represented by the following Formula(d):

wherein R^(23d) to R^(27d) each independently represent a monovalentgroup selected from a hydrogen atom, a hydrocarbon group of 1 to 10carbon atoms, an aromatic group, an unsaturated group, asulfur-containing group, an oxygen-containing group, aphosphorus-containing group, an alicyclic group, and a halogen atom.That is, 1 to 3 units of the group represented by Formula (I) may bebonded to the triazine ring.

[b] At least one of R^(20d) to R^(22d) represents a group represented bythe following Formula (d′):

wherein at least one of R^(28d) to R^(32d) represents a monovalentbonding moiety that is bonded to R^(14a) or a terminal sulfur atom ofFormula (i-2); and the others of R^(28d) to R^(32d) each independentlyrepresent a monovalent group selected from a hydrogen atom, ahydrocarbon group having 1 to 10 carbon atoms, an aromatic group, anunsaturated group, a sulfur-containing group, an oxygen-containinggroup, a phosphorus-containing group, an alicyclic group, and a halogenatom, and

the others of R^(20d) to R^(22d) each independently represent amonovalent group selected from a hydrogen atom, a hydrocarbon grouphaving 1 to 10 carbon atoms, an aromatic group, an unsaturated group, asulfur-containing group, an oxygen-containing group, aphosphorus-containing group, an alicyclic group, and a halogen atom.That is, 1 to 5 units of the group represented by Formula (I) may bebonded to the benzene ring represented by Formula (d′).

In regard to Formulae (A) to (D) and (d), in a case in which R^(16a) toR^(24a), R^(15b) to R^(24b), R^(15c) to R^(24c), and R^(20d) to R^(27d)are each a monovalent hydrocarbon group, examples of this monovalenthydrocarbon group include a linear or branched alkyl group, a linear orbranched alkenyl group, and a linear or branched alkynyl group. Specificexamples include a methyl group, an ethan-1-yl group, a propan-1-ylgroup, a 1-methylethan-1-yl group, a butan-1-yl group, a butan-2-ylgroup, a 2-methylpropan-1-yl group, a 2-methylpropan-2-yl group, apentan-1-yl group, a pentan-2-yl group, a hexan-1-yl group, aheptan-1-yl group, an octan-1-yl group, a nonan-1-yl group, and adecan-1-yl group.

In a case in which R^(16a) to R^(24a), R^(15b) to R^(24b), R^(15c) toR^(24c), and R^(20d) to R^(27d) each represent a monovalent groupselected from an aromatic group, an unsaturated group, asulfur-containing group, an oxygen-containing group, aphosphorus-containing group, an alicyclic group, and a halogen atom,specific examples thereof include the groups listed as examples in thesection [Substituents] described above.

In Formula (i-2), n represents an integer of 0 or 1, and p represents aninteger from 0 to 3, and preferably an integer of 0 or 1.

In Formula (i-2), the total number of carbon atoms of R^(11a), p unitsof R^(12a), and R^(13a) is 25 or less.

In regard to Formula (I), in a case in which R^(1a) to R^(9a) eachrepresent a group other than the monovalent sulfur-containing grouprepresented by Formula (i-1) or Formula (i-2), R^(1a) to R^(9a) eachrepresent a monovalent group selected from a hydrogen atom, ahydrocarbon group having 1 to 10 carbon atoms, an aromatic group, anunsaturated group, a sulfur-containing group, an oxygen-containinggroup, a phosphorus-containing group, an alicyclic group, and a halogenatom.

In a case in which R^(1a) to R^(9a) are each a monovalent hydrocarbongroup, examples of this monovalent hydrocarbon group include a linear orbranched alkyl group, a linear or branched alkenyl group, and a linearor branched alkynyl group. Specific examples include a methyl group, anethan-1-yl group, a propan-1-yl group, a 1-methylethan-1-yl group, abutan-1-yl group, a butan-2-yl group, a 2-methylpropan-1-yl group, a2-methylpropan-2-yl group, a pentan-1-yl group, a pentan-2-yl group, ahexan-1-yl group, a heptan-1-yl group, an octan-1-yl group, a nonan-1-ylgroup, and a decan-1-yl group. Among these, a linear or branched alkylgroup having 1 to 8 carbon atoms is preferred.

In a case in which R^(1a) to R^(9a) each represent a monovalent groupselected from an aromatic group, an unsaturated group, asulfur-containing group, an oxygen-containing group, aphosphorus-containing group, an alicyclic group, and a halogen atom,specific examples thereof include the groups listed as examples in thesection [Substituents] described above.

In regard to Formula (I), at least one of R^(1a) to R^(9a) represents amonovalent sulfur-containing group represented by Formula (i-1) orFormula (i-2). Above all, when the ease or cost of actual synthesis andheat resistance are taken into consideration, or when it is taken intoconsideration that by making the compatibility with a resin serving as amatrix satisfactory, clouding of the resin member to which the additiveof the present invention has been added can be suppressed, andmanifestation of high ultraviolet absorbency or imparting of a highrefractive index under addition of the additive in high concentrationsis enabled, it is preferable that one or two of R^(1a) to R^(9a) aremonovalent sulfur-containing groups represented by Formula (i-1) orFormula (i-2).

The position of the monovalent sulfur-containing group represented byFormula (i-1) or Formula (i-2) in Formula (I) is not particularlylimited, and the position may be the position of R^(1a), R^(3a), R^(5a),R^(7a) or R^(8a).

In regard to the additive of Formula (I) into which (i-1) has beenintroduced as the monovalent sulfur-containing group, upon consideringheat resistance and the characteristics of enabling manifestation ofhigh ultraviolet absorbency or imparting of a high refractive index whenthe additive is added in low concentrations to high concentrations, itis preferable for the monovalent sulfur-containing group represented byFormula (i-1) that m is 0, or m is 1, with R^(10a) including an alkylenegroup having 10 or fewer carbon atoms.

Furthermore, these additives have a tendency that melting points arelowered when sulfur-containing groups are introduced into the additivesand numbers of carbon atoms of each sulfur-containing groups areadjusted. When the melting point is lowered, particularly satisfactorycompatibility with a resin serving as a matrix is obtained. From thispoint of view, it is preferable that in the monovalent sulfur-containinggroup represented by Formula (i-1), m is 0, or m is 1, with R^(10a)including an alkylene group having 9 or fewer carbon atoms, and theadditive has a melting point of 91° C. or lower at normal pressure (forexample, standard atmospheric pressure: 101325 Pa).

According to another preferred embodiment, in the monovalentsulfur-containing group represented by Formula (i-1), m is 0, or m is 1,with R^(10a) including an alkylene group having 8 or fewer carbon atoms,and the additive has a melting point of below 70° C. at normal pressure.Alternatively, in the monovalent sulfur-containing group represented byFormula (i-1), m is 0, or m is 1, with R^(10a) including an alkylenegroup having 8 or fewer carbon atoms, and the additive has a meltingpoint of 35° C. or lower at normal pressure. That is, when the number ofcarbon atoms is 8 or less, and the melting point is below 70° C., evenif the additive is added in high concentrations, high transparency isobtained at large film thicknesses. Furthermore, if the additive isliquid at normal temperature (5° C. to 35° C.), high transparency can berealized even if the additive is added in high concentrations at largerfilm thicknesses.

In regard to the additive of Formula (I) into which (i-2) has beenintroduced as the monovalent sulfur-containing group, upon consideringheat resistance and the characteristics of enabling manifestation ofhigh ultraviolet absorbency or imparting of a high refractive index whenthe additive is added in low concentrations to high concentrations, itis preferable for the monovalent sulfur-containing group represented byFormula (i-2) that R^(11a) and p units of R^(12a) each includes analkylene group having 18 or fewer carbon atoms, and R^(13a) includes analkyl group having 18 or fewer carbon atoms.

These additives have a tendency that when sulfur-containing groups whichare adjusted respective numbers of carbon atoms from short chains tomedium chains are introduced into the additives, melting points arelowered. When the melting point is lowered, particularly satisfactorycompatibility with a resin serving as a matrix is obtained. When this istaken into consideration, it is preferable for the monovalentsulfur-containing group represented by Formula (i-2), R^(11a) and punits of R^(12a) each include an alkylene group having 18 or fewercarbon atoms, and R^(13a) includes an alkyl group having 18 or fewercarbon atoms, while the additive has a melting point of 91° C. or lowerat normal pressure.

In a case in which the additive has a monovalent sulfur-containing grouprepresented by Formula (i-1) or Formula (i-2) at any one position ofR^(1a) to R^(5a), according to a preferred embodiment, in the monovalentsulfur-containing group represented by Formula (i-1), m is 0, or m is 1,with R^(10a) including an alkylene group having 8 or fewer carbon atoms,or in the monovalent sulfur-containing group represented by Formula(i-2), R^(11a) and p units of R^(12a) each includes an alkylene grouphaving 8 or fewer carbon atoms, and R^(13a) includes an alkyl grouphaving 8 or fewer carbon atoms, while the additive has a melting pointof below 70° C. at normal pressure. According to a more preferredembodiment, in the monovalent sulfur-containing group represented byFormula (i-1), m is 0, or m is 1, with R^(10a) including an alkylenegroup having 8 or fewer carbon atoms, or in the monovalentsulfur-containing group represented by Formula (i-2), R^(11a) and punits of R^(12a) each includes an alkylene group having 8 or fewercarbon atoms, and R^(13a) includes an alkyl group having 8 or fewercarbon atoms, while the additive has a melting point of 35° C. or lowerat normal pressure.

(Ultraviolet Absorber that has Excellent Heat Resistance and is Intendedfor Imparting Ultraviolet Absorbency and High Refractive Index whileMaintaining Transparency of Transparent Resin Matrix)

Preferred embodiments of an ultraviolet absorber that has excellent heatresistance and is intended for imparting ultraviolet absorbency and ahigh refractive index while maintaining transparency of a transparentresin matrix, include the following.

The ultraviolet absorber has a monovalent sulfur-containing grouprepresented by Formula (i-2) at any one of the positions of R^(6a) toR^(9a), and the monovalent sulfur-containing group represented byFormula (i-2) is represented by the following formula:—S

R^(12a)—S

_(p)R^(13a)

in which p units of R^(12a) each includes an alkylene group having 1 to18 carbon atoms, while R^(13a) includes an alkyl group having 1 to 18carbon atoms.

Furthermore, p units of R^(12a) each includes an alkylene group having 1to 8 carbon atoms, and R^(13a) includes an alkyl group having 1 to 8carbon atoms, while the melting point is below 70° C. at normalpressure.

-   -   R^(13a) includes an alkyl group having 1 to 18 carbon atoms.    -   R^(13a) includes an alkyl group having 1 to 18 carbon atoms, and        the melting point is 91° C. or lower at normal pressure.    -   R^(13a) includes an alkyl group having 1 to 12 carbon atoms, and        the melting point is 91° C. or lower at normal pressure.    -   R^(13a) includes an alkyl group having 1 to 10 carbon atoms, and        the melting point is 91° C. or lower at normal pressure.    -   R^(13a) includes an alkyl group having 4 to 10 carbon atoms, and        the melting point is 91° C. or lower at normal pressure.    -   R^(13a) includes an alkyl group having 6 to 10 carbon atoms, and        the melting point is below 70° C. at normal pressure.    -   R^(13a) includes an alkyl group having 6 to 10 carbon atoms, and        the melting point is 35° C. or lower at normal pressure.    -   The substituent is selected from a methyl group, a t-butyl        group, and a hydroxyl group, while there is one or fewer t-butyl        group. Above all, the substituent is at any one of the positions        of R^(1a), R^(2a) and R^(4a), and particularly, the substituent        of R^(1a) is a hydroxyl group, the substituent of R^(2a) is a        t-butyl group, while the substituent of R^(4a) is a methyl        group.

(Ultraviolet Absorber that Absorbs Light in Long Wavelength Region andSuppresses Yellowing of Transparent Resin Matrix)

An ultraviolet absorber that absorbs light in the long wavelength regionand suppresses yellowing of a transparent resin matrix according to apreferred embodiment has a monovalent sulfur-containing grouprepresented by Formula (i-2) at any one of the positions of R^(6a) toR^(9a), and the monovalent sulfur-containing group represented byFormula (i-2) is represented by the following formula:—S

R^(12a)—S

_(p)R^(13a)wherein R^(12a), R^(13a) and p respectively have the same meanings asdescribed above.

The additive of Formula (I) has a high solubility in resin monomers,does not separate from the surface even if the resin matrix is processedinto a plastic lens, and the plastic lens has high transparency, and dueto its optical characteristics, the plastic lens can sufficiently absorblight in the wavelength region of up to 250 to 420 nm. Furthermore, theadditive has a high ultraviolet absorption effect (molar extinctioncoefficient), and can sufficiently absorb light of the wavelengths evenif added in a small amount. Since the slope of an absorption peak of theadditive at 350 to 390 nm in a chloroform solution is larger than thatof conventional ultraviolet absorbers, yellowing of the resin member canbe suppressed.

Also, in order to obtain a resin member having excellent externalappearance with suppressed yellowing, which absorbs harmful light in thewavelength region of up to 400 to 420 nm that has a potential of causingdisorders in the eye tissues, such as age-related macular degeneration,and suppresses the absorption of light having a wavelength in thevicinity of 420 nm or larger that causes yellowing of a lens, it ispreferable that the light absorption peak in a 100 μM chloroformsolution is found at 350 to 390 nm, more preferably at 360 to 380 nm,and particularly preferably at 360 to 375 nm. Furthermore, it ispreferable that an absorption peak in those wavelength regions is themaximum absorption wavelength (λ_(max)). Furthermore, regarding thewavelength peak, in order to suppress absorption of light having alonger wavelength than near 420 nm, it is desirable that the absorptionspectrum on the longer wavelength side is sharp (the absolute value ofthe slope is large), and the slope on the longer wavelength side of theabsorption peak (absolute value of the slope of a straight lineconnecting the absorption peak and the peak end of the absorptionspectrum on the longer wavelength side; see FIG. 3 and Examplesdescribed below) is preferably 0.025 or larger, and more preferably0.030 or larger. Furthermore, in order to efficiently absorb light witha small amount of the additive, the molar absorption coefficient(maximum molar absorption coefficient: ε_(λmax)) of the absorption peakat 350 to 390 nm is preferably 17,000 L/(mol·cm) or larger, morepreferably 18,000 L/(mol·cm) or larger, and particularly preferably20,000 L/(mol·cm) or larger.

2. Additive Represented by Formula (II)

An additive represented by Formula (II) described above contains theabove-described monovalent sulfur-containing group represented byFormula (ii-1) or (ii-2) in a benzophenone-based skeleton.

In regard to Formula (ii-1), R^(11b) represents a divalent hydrocarbongroup having 1 to 12 carbon atoms which may be substituted a hydrogenatom with, interrupted at least any one of two terminals by orinterrupted a carbon-carbon bond by a monovalent or divalent groupselected from an aromatic group, an unsaturated group, asulfur-containing group, an oxygen-containing group, aphosphorus-containing group, an alicyclic group and a halogen atom.

Examples of the divalent hydrocarbon group of R^(11b) include a linearor branched alkylene group, an alkenylene group, and an alkynylenegroup. Specific examples include a methylene group, an ethane-1,2-diylgroup, a propane-1,3-diyl group, a 1-methylethane-1,2-diyl group, abutane-1,4-diyl group, a butane-1,3-diyl group, a2-methylpropane-1,3-diyl group, a pentane-1,5-diyl group, apentane-1,4-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diylgroup, an octane-1,8-diyl group, a nonane-1,9-diyl group, adecane-1,10-diyl group, an undecane-1,11-diyl group, and adodecane-1,12-diyl group.

In a case in which the divalent hydrocarbon group is substituted ahydrogen atom with, interrupted at least any one of two terminals by orinterrupted a carbon-carbon bond by the monovalent or divalent group,the number of the monovalent or divalent groups is preferably 2 or less,and more preferably 1 or less.

Specific examples of the aromatic group, unsaturated group,sulfur-containing group, oxygen-containing group, phosphorus-containinggroup, alicyclic group and halogen atom of the monovalent or divalentgroup include the groups listed as examples in the section[Substituents] described above.

In regard to Formula (ii-1), q represents an integer of 0 or 1.

In regard to Formula (ii-2), R^(12b) represents a divalent hydrocarbongroup having 1 to 20 carbon atoms which may be substituted a hydrogenatom with, interrupted at least any one of two terminals by orinterrupted a carbon-carbon bond by a monovalent or divalent groupselected from an aromatic group, an unsaturated group, asulfur-containing group, an oxygen-containing group, aphosphorus-containing group, an alicyclic group and a halogen atom.

Examples of the divalent hydrocarbon group of R^(12b) include a linearor branched alkylene group, a linear or branched alkenylene group, and alinear or branched alkynylene group. Specific examples include amethylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, a1-methylethane-1,2-diyl group, a butane-1,4-diyl group, abutane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, apentane-1,5-diyl group, a pentane-1,4-diyl group, a hexane-1,6-diylgroup, a heptane-1,7-diyl group an octane-1,8-diyl group, anonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diylgroup, a dodecane-1,12-diyl group, a tridecan-1,13-yl group, atetradecan-1,14-yl group, a pentadecan-1,15-yl group, ahexadecan-1,16-yl group, a heptadecan-1,17-yl group, anoctadecan-1,18-yl group, a nonadecan-1,19-yl group, and aneicosan-1,20-yl group. Among these, an alkylene group is preferred, anda linear alkylene group is more preferred.

In a case in which the divalent hydrocarbon group of R^(12b) issubstituted a hydrogen atom with, interrupted at least any one of twoterminals by or interrupted a carbon-carbon bond by the monovalent ordivalent group, the number of the monovalent or divalent groups ispreferably 2 or less, and more preferably 1 or less.

Specific examples of the aromatic group, unsaturated group,sulfur-containing group, oxygen-containing group, phosphorus-containinggroup, alicyclic group, and halogen atom of the monovalent or divalentgroup include the groups listed as examples in the section[Substituents] described above.

In regard to Formula (ii-2), in a case in which s of R^(13b) is 2 orlarger, R^(13b)'s each independently represent a divalent hydrocarbongroup having 1 to 20 carbon atoms which may be substituted a hydrogenatom with, interrupted at least any one of two terminals by orinterrupted a carbon-carbon bond by a monovalent or divalent groupselected from an aromatic group, an unsaturated group, asulfur-containing group, an oxygen-containing group, aphosphorus-containing group, an alicyclic group and a halogen atom.

Examples of the divalent hydrocarbon group of R^(13b) include the groupslisted above as examples of the divalent hydrocarbon groups of R^(12b).Among these, an alkylene group is preferred, and a linear alkylene groupis more preferred.

In a case in which the divalent hydrocarbon group of R^(13b) which maybe substituted a hydrogen atom with, interrupted at least any one of twoterminals by or interrupted a carbon-carbon bond by the monovalent ordivalent group, the number of the monovalent or divalent groups ispreferably 2 or less, and more preferably 1 or less.

Specific examples of the aromatic group, unsaturated group,sulfur-containing group, oxygen-containing group, phosphorus-containinggroup, alicyclic group, and halogen atom of the monovalent or divalentgroup include the groups listed as examples in the section[Substituents] described above.

In regard to Formula (ii-2), R^(14b) represents a monovalent hydrocarbongroup having 1 to 20 carbon atoms which may be substituted a hydrogenatom with, interrupted a proximal terminal by or interrupted acarbon-carbon bond by a monovalent or divalent group selected from anaromatic group, an unsaturated group, a sulfur-containing group, anoxygen-containing group, a phosphorus-containing group, an alicyclicgroup and a halogen atom.

Examples of the monovalent hydrocarbon group of R^(14b) include a linearor branched alkyl group, a linear or branched alkenyl group, and alinear or branched alkynyl group. Specific examples include a methylgroup, an ethan-1-yl group, a propan-1-yl group, a 1-methylethan-1-ylgroup, a butan-1-yl group, a butan-2-yl group, a 2-methylpropan-1-ylgroup, a 2-methylpropan-2-yl group, a pentan-1-yl group, a pentan-2-ylgroup, a hexan-1-yl group, a heptan-1-yl group, an octan-1-yl group, anonan-1-yl group, a decan-1-yl group, an undecan-1-yl group, adodecan-1-yl group, a tridecan-1-yl group, a tetradecan-1-yl group, apentadecan-1-yl group, a hexadecan-1-yl group, a heptadecan-1-yl group,an octadecan-1-yl group, a nonadecan-1-yl group, and an eicosan-1-ylgroup. Among these, an alkyl group is preferred, and a linear alkylgroup is more preferred.

In a case in which the monovalent hydrocarbon group of R^(14b) issubstituted a hydrogen atom with, interrupted a proximal terminal by orinterrupted a carbon-carbon bond by the monovalent or divalent group,the number of the monovalent or divalent groups is preferably 2 or less,and more preferably 1 or less.

Specific examples of the aromatic group, unsaturated group,sulfur-containing group, oxygen-containing group, phosphorus-containinggroup, alicyclic group, and halogen atom of the monovalent or divalentgroup include the groups listed as examples in the section[Substituents] described above.

In regard to Formula (ii-2), r represents an integer of 0 or 1, and srepresents an integer from 0 to 3, and preferably 0 or 1.

In regard to Formula (ii-2), the total number of carbon atoms ofR^(12b), s units of R^(13b), and R^(14b) is 25 or less.

In regard to Formula (II), in a case in which R^(1b) to R^(10b) eachrepresent a group other than the monovalent sulfur-containing grouprepresented by Formula (ii-1) or Formula (ii-2), R^(1b) to R^(10b) eachrepresent a monovalent group selected from a hydrogen atom, a monovalenthydrocarbon group having 1 to 10 carbon atoms, an aromatic group, anunsaturated group, a sulfur-containing group, an oxygen-containinggroup, a phosphorus-containing group, an alicyclic group, and a halogenatom.

In a case in which R^(1b) to R^(10b) each represent a monovalenthydrocarbon group, examples of this monovalent hydrocarbon group includea linear or branched alkyl group, a linear or branched alkenyl group,and a linear or branched alkynyl group. Specific examples include amethyl group, an ethan-1-yl group, a propan-1-yl group, a1-methylethan-1-yl group, a butan-1-yl group, a butan-2-yl group, a2-methylpropan-1-yl group, a 2-methylpropan-2-yl group, a pentan-1-ylgroup, a pentan-2-yl group, a hexan-1-yl group, a heptan-1-yl group, anoctan-1-yl group, a nonan-1-yl group, and a decan-1-yl group. Amongthese, a linear or branched alkyl group having 1 to 8 carbon atoms ispreferred.

In a case in which R^(1b) to R^(10b) each represent a monovalent groupselected from an aromatic group, an unsaturated group, asulfur-containing group, an oxygen-containing group, aphosphorus-containing group, an alicyclic group, and a halogen atom,specific examples thereof include the groups listed as examples in thesection [Substituents] described above.

In regard to Formula (II), at least one of R^(1b) to R^(10b) representsa monovalent sulfur-containing group represented by Formula (ii-1) orFormula (ii-2). Above all, when the ease of actual synthesis, productioncost and heat resistance are taken into consideration, or when it isconsidered that by improving the compatibility with a resin serving as amatrix, clouding of the resin member to which the additive of thepresent invention has been added can be suppressed, and manifestation ofhigh ultraviolet absorbency or imparting of a high refractive indexunder addition of the additive in high concentrations is enabled, it ispreferable that one or two of R^(1b) to R^(10b) are monovalentsulfur-containing groups represented by Formula (ii-1) or Formula(ii-2).

The position of the monovalent sulfur-containing group represented byFormula (ii-1) or Formula (ii-2) in Formula (II) is not particularlylimited, and the position may be the position of R^(3b) or R^(8b).

3. Additive Represented by Formula (III)

An additive represented by Formula (III) described above contains theabove-described monovalent sulfur-containing group represented byFormula (iii-1) or (iii-2) in a salicylate-based skeleton.

In regard to Formula (iii-1), R^(11c) represents a divalent hydrocarbongroup having 1 to 12 carbon atoms, which may have a hydrogen atomsubstituted with a monovalent or divalent group selected from anaromatic group, an unsaturated group, a sulfur-containing group, anoxygen-containing group, a phosphorus-containing group, an alicyclicgroup and a halogen atom, which may have at least any one of twoterminals interrupted by the monovalent or divalent group, or which mayhave a carbon-carbon bond interrupted by the monovalent or divalentgroup.

Examples of the divalent hydrocarbon group of R^(11c) include a linearor branched alkylene group, an alkenylene group, and an alkynylenegroup. Specific examples include a methylene group, an ethane-1,2-diylgroup, a propane-1,3-diyl group, a 1-methylethane-1,2-diyl group, abutane-1,4-diyl group, a butane-1,3-diyl group, a2-methylpropane-1,3-diyl group, a pentane-1,5-diyl group, apentane-1,4-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diylgroup, an octane-1,8-diyl group, a nonane-1,9-diyl group, adecane-1,10-diyl group, an undecane-1,11-diyl group, and adodecane-1,12-diyl group.

In a case in which the divalent hydrocarbon group of R^(11c) has ahydrogen atom substituted with the monovalent or divalent group, has atleast any one of two terminals interrupted by the monovalent or divalentgroup, or has a carbon-carbon bond interrupted by the monovalent ordivalent group, the number of the monovalent or divalent groups ispreferably 2 or less, and more preferably 1 or less.

Specific examples of the aromatic group, unsaturated group,sulfur-containing group, oxygen-containing group, phosphorus-containinggroup, alicyclic group, and halogen atom of the monovalent or divalentgroup include the groups listed as examples in the section[Substituents] described above.

In regard to Formula (iii-1), t represents an integer of 0 or 1.

In regard to Formula (iii-2), R^(12c) represents a divalent hydrocarbongroup having 1 to 20 carbon atoms, which may have a hydrogen atomsubstituted with a monovalent or divalent group selected from anaromatic group, an unsaturated group, a sulfur-containing group, anoxygen-containing group, a phosphorus-containing group, an alicyclicgroup and a halogen atom, which may have at least any one of twoterminals interrupted by the monovalent or divalent group, or which mayhave a carbon-carbon bond interrupted by the monovalent or divalentgroup.

Examples of the divalent hydrocarbon group of R^(12c) include a linearor branched alkylene group, a linear or branched alkenylene group, and alinear or branched alkynylene group. Specific examples include amethylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, a1-methylethane-1,2-diyl group, a butane-1,4-diyl group, abutane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, apentane-1,5-diyl group, a pentane-1,4-diyl group, a hexane-1,6-diylgroup, a heptane-1,7-diyl group, an octane-1,8-diyl group, anonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diylgroup, a dodecane-1,12-diyl group, a tridecan-1,13-yl group, atetradecan-1,14-yl group, a pentadecan-1,15-yl group, ahexadecan-1,16-yl group, a heptadecan-1,17-yl group, anoctadecan-1,18-yl group, a nonadecan-1,19-yl group, and aneicosan-1,20-yl group. Among these, an alkylene group is preferred, anda linear alkylene group is more preferred.

In a case in which the divalent hydrocarbon group of R^(12c) has ahydrogen atom substituted with the monovalent or divalent group, has atleast any one of two terminals interrupted by the monovalent or divalentgroup, or has a carbon-carbon bond interrupted by the monovalent ordivalent group, the number of the monovalent or divalent groups ispreferably 2 or less, and more preferably 1 or less.

Specific examples of the aromatic group, unsaturated group,sulfur-containing group, oxygen-containing group, phosphorus-containinggroup, alicyclic group, and halogen atom of the monovalent or divalentgroup include the groups listed as examples in the section[Substituents] described above.

In regard to Formula (iii-2), in a case in which v is 2 or larger,R^(13c)'s each independently represent a divalent hydrocarbon grouphaving 1 to 20 carbon atoms which may be substituted a hydrogen atomwith, interrupted at least any one of two terminals by or interrupted acarbon-carbon bond by a monovalent or divalent group selected from anaromatic group, an unsaturated group, a sulfur-containing group, anoxygen-containing group, a phosphorus-containing group, an alicyclicgroup and a halogen atom.

Examples of the divalent hydrocarbon group of R^(13c) include the groupslisted above as examples of the divalent hydrocarbon group of R^(12c).Among these, an alkylene group is preferred, and a linear alkylene groupis more preferred.

In a case in which the divalent hydrocarbon group of R^(13c) issubstituted a hydrogen atom with, interrupted at least any one of twoterminals by or interrupted a carbon-carbon bond by the monovalent ordivalent group, the number of the monovalent or divalent groups ispreferably 2 or less, and more preferably 1 or less.

Specific examples of the aromatic group, unsaturated group,sulfur-containing group, oxygen-containing group, phosphorus-containinggroup, alicyclic group, and halogen atom of the monovalent or divalentgroup include the groups listed as examples in the section[Substituents] described above.

In regard to Formula (iii-2), R^(14c) represents a monovalenthydrocarbon group having 1 to 20 carbon atoms which may be substituted ahydrogen atom with, interrupted a proximal terminal by or interrupted acarbon-carbon bond by a monovalent or divalent group selected from anaromatic group, an unsaturated group, a sulfur-containing group, anoxygen-containing group, a phosphorus-containing group, an alicyclicgroup and a halogen atom.

Examples of the monovalent hydrocarbon group of R^(14c) include a linearor branched alkyl group, a linear or branched alkenyl group, and alinear or branched alkynyl group. Specific examples include a methylgroup, an ethan-1-yl group, a propan-1-yl group, a 1-methylethan-1-ylgroup, a butan-1-yl group, a butan-2-yl group, a 2-methylpropan-1-ylgroup, a 2-methylpropan-2-yl group, a pentan-1-yl group, a pentan-2-ylgroup, a hexan-1-yl group, a heptan-1-yl group, an octan-1-yl group, anonan-1-yl group, a decan-1-yl group, an undecan-1-yl group, adodecan-1-yl group, a tridecan-1-yl group, a tetradecan-1-yl group, apentadecan-1-yl group, a hexadecan-1-yl group, a heptadecan-1-yl group,an octadecan-1-yl group, a nonan-1-yl group, and an eicosan-1-yl group.Among these, an alkyl group is preferred, and a linear alkyl group ismore preferred.

In a case in which the monovalent hydrocarbon group of R^(14c) issubstituted a hydrogen atom with, interrupted a proximal terminal by orinterrupted a carbon-carbon bond by the monovalent or divalent group,the number of the monovalent or divalent groups is preferably 2 or less,and more preferably 1 or less.

Specific examples of the aromatic group, unsaturated group,sulfur-containing group, oxygen-containing group, phosphorus-containinggroup, alicyclic group, and halogen atom of the monovalent or divalentgroup include the groups listed as examples in the section[Substituents] described above.

In regard to Formula (iii-2), u represents an integer of 0 or 1, and vrepresents an integer from 0 to 3, and preferably 0 or 1.

In regard to Formula (iii-2), the total number of carbon atoms ofR^(12c), v units of R^(13c), and R^(14c) is 25 or less.

In regard to Formula (III), in a case in which R^(1c) to R^(10c) areeach a group other than a monovalent sulfur-containing group representedby Formula (iii-1) or Formula (iii-2), R^(1c) to R^(10c) each representa monovalent group selected from a hydrogen atom, a hydrocarbon grouphaving 1 to 10 carbon atoms, an aromatic group, an unsaturated group, asulfur-containing group, an oxygen-containing group, aphosphorus-containing group, an alicyclic group, and a halogen atom.

In a case in which R^(1c) to R^(10c) each represent a monovalenthydrocarbon group, examples of this monovalent hydrocarbon group includea linear or branched alkyl group, a linear or branched alkenyl group,and a linear or branched alkynyl group. Specific examples include amethyl group, an ethan-1-yl group, a propan-1-yl group, a1-methylethan-1-yl group, a butan-1-yl group, a butan-2-yl group, a2-methylpropan-1-yl group, a 2-methylpropan-2-yl group, a pentan-1-ylgroup, a pentan-2-yl group, a hexan-1-yl group, a heptan-1-yl group, anoctan-1-yl group, a nonan-1-yl group, and a decan-1-yl group. Amongthese, a linear or branched alkyl group having 1 to 8 carbon atoms ispreferred.

In a case in which R^(1c) to R^(10c) each represent an aromatic group,an unsaturated group, a sulfur-containing group, an oxygen-containinggroup, a phosphorus-containing group, an alicyclic group, or a halogenatom, specific examples thereof include the groups listed as examples inthe section [Substituents] described above.

In regard to Formula (III), at least one of R^(1c) to R^(10c) is amonovalent sulfur-containing group represented by Formula (iii-1) or(Formula iii-2). Above all, when the ease or cost of actual synthesisand heat resistance are taken into consideration, or when it is takeninto consideration that by making the compatibility with a resin servingas a matrix satisfactory, clouding of the resin member to which theadditive of the present invention has been added can be suppressed, andmanifestation of high ultraviolet absorbency or imparting of a highrefractive index under addition of the additive in high concentrationsis enabled, it is preferable that one or two of R^(1c) to R^(10c) aremonovalent sulfur-containing groups represented by Formula (iii-1) orFormula (iii-2).

The position of the monovalent sulfur-containing group represented byFormula (iii-1) or Formula (iii-2) in Formula (III) is not particularlylimited, and the position may be the position of R^(7c) or R^(9c).

In regard to the additives of Formulae (II) and (III), into which (ii-1)to (iii-1) have been introduced as monovalent sulfur-containing groups,upon considering heat resistance and the characteristics of enablingmanifestation of high ultraviolet absorbency or imparting of a highrefractive index when the additive is added in low concentrations tohigh concentrations, it is preferable that for the monovalentsulfur-containing group represented by Formula (ii-1), q is 0, or q is1, with R^(11b) including an alkylene group having 10 or fewer carbonatoms, and for the monovalent sulfur-containing group represented byFormula (iii-1), t is 0, or t is 1, with R^(11c) including an alkylenegroup having 10 or fewer carbon atoms.

Compatibility with a resin serving as a matrix (transparency) isdependent on, in view of the structure of the additive, the number ofcarbon atoms of an alkyl group among the functional groups of Formula(i-v-1) and Formula (i-v-2) in the benzotriazole, benzophenone,salicylate and triazine skeletons in Formulae (I), (II), (III), (IV) and(V), and in view of properties, the melting point. However, regardingthe melting point, there is no clear correlation between the number ofcarbon atoms of Formula (i-v-1) and Formula (i-v-2) and the meltingpoint, and it is difficult to achieve a balance between the two factors,structure and properties.

These additives have a tendency that when the respective numbers ofcarbon atoms are adjusted by introducing sulfur-containing groups intothe additives, melting points are lowered. When the melting point islowered, particularly satisfactory compatibility with a resin serving asa matrix is obtained. From this point of view, it is preferable that forthe monovalent sulfur-containing group represented by Formula (ii-1), qis 0, or q is 1, with R^(11b) including an alkylene group having 9 orfewer carbon atoms, and for the monovalent sulfur-containing grouprepresented by (iii-1), t is 0, or t is 1, with R^(11c) including analkylene group having 9 or fewer carbon atoms, while the melting pointis 91° C. or lower at normal pressure (for example, standard atmosphericpressure 101325 Pa).

According to another preferred embodiment, the monovalentsulfur-containing group represented by Formula (ii-1) is such that q is0, or q is 1, with R^(11b) including an alkylene group having 8 or fewercarbon atoms, and the monovalent sulfur-containing group represented byFormula (iii-1) is such that t is 0, or t is 1, with R^(11c) includingan alkylene group having 8 or fewer carbon atoms, while the meltingpoint is below 70° C. at normal pressure. Alternatively, the monovalentsulfur-containing group represented by Formula (ii-1) is such that q is0, or q is 1, with R^(11b) including an alkylene group having 8 or fewercarbon atoms, and the monovalent sulfur-containing group represented byFormula (iii-1) is such that t is 0, or t is 1, with R^(11c) includingan alkylene group having 8 or fewer carbon atoms, while the meltingpoint is 35° C. or lower at normal pressure. That is, when the number ofcarbon atoms is 8 or less, and the melting point is below 70° C., evenif the additive is added in high concentrations, high transparency isobtained at large film thicknesses. Furthermore, if the additive isliquid at normal temperature (5° C. to 35° C.), high transparency can berealized even if the additive is added in high concentrations at largerfilm thicknesses.

Regarding the additives of Formulae (II) and (III) into which (ii-2) to(iii-2) have been introduced as monovalent sulfur-containing groups,when it is taken into consideration that manifestation of highultraviolet absorbency or imparting of a high refractive index isenabled through addition in low concentrations to high concentrations,it is preferable that for the monovalent sulfur-containing grouprepresented by Formula (ii-2), R^(12b) and s units of R^(13b) eachincludes an alkylene group having 18 or fewer carbon atoms, with R^(14b)including an alkyl group having 18 or fewer carbon atoms, and for themonovalent sulfur-containing group represented by Formula (iii-2),R^(12c) and v units of R^(13c) each includes an alkylene group having 18or fewer carbon atoms, with R^(14c) including an alkyl group having 18or fewer carbon atoms.

Furthermore, these additives have a tendency that when the respectivenumbers of carbon atoms are adjusted from short chain to medium chainsby introducing sulfur-containing groups into the additives, meltingpoints are lowered. When the melting point is lowered, particularlysatisfactory compatibility with a resin serving as a matrix is obtained.When this is taken into consideration, it is preferable that for themonovalent sulfur-containing group represented by Formula (ii-2),R^(12b) and s units of R^(13b) each includes an alkylene group having 18or fewer carbon atoms, with R^(14b) including an alkyl group having 18or fewer carbon atoms, and for the monovalent sulfur-containing grouprepresented by Formula (iii-2), R^(12c) and v units of R^(13c) eachincludes an alkylene group having 18 or fewer carbon atoms, with R^(14c)including an alkyl group having 18 or fewer carbon atoms, while themelting point is 91° C. or lower at normal pressure.

According to another preferred embodiment, the monovalentsulfur-containing group represented by Formula (ii-2) is such thatR^(12b) and s units of R^(13b) each includes an alkylene group having 8or fewer carbon atoms, with R^(14b) including an alkyl group having 8 orfewer carbon atoms, and the monovalent sulfur-containing grouprepresented by Formula (iii-2) is such that R^(12c) and v units ofR^(13c) each includes an alkylene group having 8 or fewer carbon atoms,with R^(14c) including an alkyl group having 8 or fewer carbon atoms,while the melting point is below 70° C. at normal pressure.Alternatively, the monovalent sulfur-containing group represented byFormula (ii-2) is such that R^(12b) and s units of R^(13b) each includesan alkylene group having 8 or fewer carbon atoms, with R^(14b) includingan alkyl group having 8 or fewer carbon atoms, and the monovalentsulfur-containing group represented by Formula (iii-2) is such thatR^(12c) and v units of R^(13c) each includes an alkylene group having 8or fewer carbon atoms, with R^(14c) including an alkyl group having 8 orfewer carbon atoms, while the melting point is 35° C. or lower at normalpressure. That is, when the number of carbon atoms is 8 or less, and themelting point is below 70° C., even if the additive is added in highconcentrations, high transparency is obtained at large film thicknesses.Furthermore, if the additive is liquid at normal temperature (5° C. to35° C.), high transparency can be realized even if the additive is addedin high concentrations at larger film thicknesses.

4. Additive Represented by Formula (IV)

An additive represented by Formula (IV) described above contains theabove-described monovalent sulfur-containing group represented byFormula (iv-1) or (iv-2) in a triazine-based skeleton.

The additive represented by Formula (IV) may be solid or may be liquid,and when a monovalent sulfur-containing group is introduced thereinto,heat resistance is increased, particularly satisfactory compatibilitywith a resin serving as a matrix is obtained, and even if the additiveis added in high concentrations, high transparency is obtained.

In regard to Formula (iv-1), R^(16d) represents a divalent hydrocarbongroup having 1 to 12 carbon atoms which may be substituted a hydrogenatom with, interrupted at least any one of two terminals by orinterrupted a carbon-carbon bond by a monovalent or divalent groupselected from an aromatic group, an unsaturated group, asulfur-containing group, an oxygen-containing group, aphosphorus-containing group, an alicyclic group and a halogen atom.

Examples of the divalent hydrocarbon group of R^(16d) include a linearor branched alkylene group, an alkenylene group, and an alkynylenegroup. Specific examples include a methylene group, an ethane-1,2-diylgroup, a propane-1,3-diyl group, a 1-methylethane-1,2-diyl group, abutane-1,4-diyl group, a butane-1,3-diyl group, a2-methylpropane-1,3-diyl group, a pentane-1,5-diyl group, apentane-1,4-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diylgroup, an octane-1,8-diyl group, a nonane-1,9-diyl group, adecane-1,10-diyl group, an undecane-1,11-diyl group, and adodecane-1,12-diyl group.

In a case in which the divalent hydrocarbon group of R^(16d) issubstituted a hydrogen atom with, interrupted at least any one of twoterminals by or interrupted a carbon-carbon bond by the monovalent ordivalent group, the number of the monovalent or divalent groups ispreferably 2 or less, and more preferably 1 or less.

Specific examples of the aromatic group, unsaturated group,sulfur-containing group, oxygen-containing group, phosphorus-containinggroup, alicyclic group, and halogen atom of the monovalent or divalentgroup include the groups listed as examples in the section[Substituents] described above.

Among these, when it is considered that by improving the compatibilitywith a resin serving as a matrix, clouding of the resin member to whichthe additive of the present invention has been added can be suppressed,and manifestation of high ultraviolet absorbency or imparting of a highrefractive index under addition of the additive in high concentrationsis enabled, a divalent hydrocarbon group having 1 to 9 carbon atoms ispreferred, and a divalent hydrocarbon group having 1 to 8 carbon atomsis more preferred. Furthermore, when this is taken into consideration,an embodiment in which w=0, that is, Formula (iv-1) represents —SH, isalso similarly preferable. Among the hydrocarbon groups, an alkylenegroup is preferred, and the monovalent sulfur-containing grouprepresented by Formula (iv-1) according to a preferred embodiment issuch that w is 0, or w is 1, with R^(16d) including an alkylene grouphaving 8 or fewer carbon atoms. The alkylene group is particularlypreferably a linear alkylene group.

In regard to Formula (iv-1), w represents an integer of 0 or 1.

In regard to Formula (iv-2), R^(17d) represents a divalent hydrocarbongroup having 1 to 20 carbon atoms which may be substituted a hydrogenatom with, interrupted at least any one of two terminals by orinterrupted a carbon-carbon bond by a monovalent or divalent groupselected from an aromatic group, an unsaturated group, asulfur-containing group, an oxygen-containing group, aphosphorus-containing group, an alicyclic group and a halogen atom.

Examples of the divalent hydrocarbon group of R^(17d) include a linearor branched alkylene group, a linear or branched alkenylene group, and alinear or branched alkynylene group. Specific examples include amethylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, a1-methylethane-1,2-diyl group, a butane-1,4-diyl group, abutane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, apentane-1,5-diyl group, a pentane-1,4-diyl group, a hexane-1,6-diylgroup, a heptane-1,7-diyl group, an octane-1,8-diyl group, anonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diylgroup, a dodecane-1,12-diyl group, a tridecan-1,13-yl group, atetradecan-1,14-yl group, a pentadecan-1,15-yl group, ahexadecan-1,16-yl group, a heptadecan-1,17-yl group, anoctadecan-1,18-yl group, a nonadecan-1,19-yl group, and aneicosan-1,20-yl group. Among these, an alkylene group is preferred, anda linear alkylene group is more preferred.

In a case in which the divalent hydrocarbon group of R^(17d) issubstituted a hydrogen atom with, interrupted at least any one of twoterminals by or interrupted a carbon-carbon bond by the monovalent ordivalent group, the number of the monovalent or divalent groups ispreferably 2 or less, and more preferably 1 or less.

Specific examples of the aromatic group, unsaturated group,sulfur-containing group, oxygen-containing group, phosphorus-containinggroup, alicyclic group, halogen atom of the monovalent or divalent groupinclude the groups listed as examples in the section [Substituents]described above.

In regard to Formula (iv-2), in a case in which y of R^(18d) is 2 orlarger, R^(18d)'s each independently represent a divalent hydrocarbongroup having 1 to 20 carbon atoms which may be substituted a hydrogenatom with, interrupted at least any one of two terminals by orinterrupted a carbon-carbon bond by a monovalent or divalent groupselected from an aromatic group, an unsaturated group, asulfur-containing group, an oxygen-containing group, aphosphorus-containing group, an alicyclic group and a halogen atom.

Examples of the divalent hydrocarbon group of R^(18d) include the groupslisted above as examples of the divalent hydrocarbon group of R^(17d).Among these, an alkylene group is preferred, and a linear alkylene groupis more preferred.

In a case in which the divalent hydrocarbon group of R^(18d) issubstituted a hydrogen atom with, interrupted at least any one of twoterminals by or interrupted a carbon-carbon bond by the monovalent ordivalent group, the number of the monovalent or divalent groups ispreferably 2 or less, and more preferably 1 or less.

Specific examples of the aromatic group, unsaturated group,sulfur-containing group, oxygen-containing group, phosphorus-containinggroup, alicyclic group, and halogen atom of the monovalent or divalentgroup include the groups listed as examples in the section[Substituents] described above.

In regard to Formula (iv-2), R^(19d) represents a monovalent hydrocarbongroup having 1 to 20 carbon atoms which may be substituted a hydrogenatom with, interrupted a proximal terminal by or interrupted acarbon-carbon bond by a monovalent or divalent group selected from anaromatic group, an unsaturated group, a sulfur-containing group, anoxygen-containing group, a phosphorus-containing group, an alicyclicgroup and a halogen atom.

Examples of the monovalent hydrocarbon group of R^(19d) include a linearor branched alkyl group, a linear or branched alkenyl group, and alinear or branched alkynyl group. Specific examples include a methylgroup, an ethan-1-yl group, a propan-1-yl group, a 1-methylethan-1-ylgroup, a butan-1-yl group, a butan-2-yl group, a 2-methylpropan-1-ylgroup, a 2-methylpropan-2-yl group, a pentan-1-yl group, a pentan-2-ylgroup, a hexan-1-yl group, a heptan-1-yl group, an octan-1-yl group, anonan-1-yl group, a decan-1-yl group, an undecan-1-yl group, adodecan-1-yl group, a tridecan-1-yl group, a tetradecan-1-yl group, apentadecan-1-yl group, a hexadecan-1-yl group, a heptadecan-1-yl group,an octadecan-1-yl group, a nonan-1-yl group, and an eicosan-1-yl group.Among these, an alkyl group is preferred, and a linear alkyl group ismore preferred.

In a case in which the monovalent hydrocarbon group of R^(19d) issubstituted a hydrogen atom with, interrupted a proximal terminal by orinterrupted a carbon-carbon bond by the monovalent or divalent group,the number of substituents is preferably 2 or less, and more preferably1 or less.

Specific examples of the aromatic group, unsaturated group,sulfur-containing group, oxygen-containing group, phosphorus-containinggroup, alicyclic group, and halogen atom of the monovalent or divalentgroup include the groups listed as examples in the section[Substituents] described above.

In regard to Formula (iv-2), x represents an integer of 0 or 1, and yrepresents an integer from 0 to 3, and preferably 0 or 1.

In regard to Formula (iv-2), the total number of carbon atoms ofR^(17d), y units of R^(18d), and R^(19d) is preferably 54 or less, morepreferably 36 or less, and particularly preferably 25 or less. Aboveall, when it is considered that by improving the compatibility with aresin serving as a matrix, clouding of the resin member to which theadditive of the present invention has been added can be suppressed, andmanifestation of high ultraviolet absorbency or imparting of a highrefractive index under addition of the additive in high concentrationsis enabled, it is preferable that the monovalent sulfur-containing grouprepresented by Formula (iv-2) is such that R^(17d) and y units ofR^(18d) each include an alkylene group having 18 or fewer carbon atoms,while R^(19d) is an alkyl group having 18 or fewer carbon atoms; it ismore preferable that R^(17d) and y units of R^(18d) each include analkylene group having 12 or fewer carbon atoms, while R^(19d) is analkyl group having 12 or fewer carbon atoms; and it is particularlypreferable that R^(17d) and y units of R^(18d) each include an alkylenegroup having 8 or fewer carbon atoms, while R^(19d) is an alkyl grouphaving 8 or fewer carbon atoms. Furthermore, it is preferable thatR^(17d), y units of R^(18d), and R^(19d) are all straight chains, andR^(17d), R^(18d) and R^(19d) each have 1 to 18 carbon atoms. It is morepreferable that R^(17d), R^(18d), and R^(19d) each have 1 to 12 carbonatoms, and it is even more preferable that R^(17d), R^(18d), and R^(19d)each have 1 to 8 carbon atoms, still more preferably 1 to 6 carbonatoms, and particularly preferably one carbon atom (here, the case inwhich x=0, and the case in which y=0 are also included).

In regard to Formula (IV), in a case in which R^(1d) to R^(15d) eachrepresent a group other than the monovalent sulfur-containing grouprepresented by Formula (iv-1) or Formula (iv-2), R^(1d) to R^(15d) eachrepresent a monovalent group selected from a hydrogen atom, ahydrocarbon group having 1 to 10 carbon atoms, an aromatic group, anunsaturated group, a sulfur-containing group, an oxygen-containinggroup, a phosphorus-containing group, an alicyclic group, and a halogenatom.

In a case in which R^(1d) to R^(15d) each represent a monovalenthydrocarbon group, examples of this monovalent hydrocarbon group includea linear or branched alkyl group, a linear or branched alkenyl group,and a linear or branched alkynyl group. Specific examples include amethyl group, an ethan-1-yl group, a propan-1-yl group, a1-methylethan-1-yl group, a butan-1-yl group, a butan-2-yl group, a2-methylpropan-1-yl group, a 2-methylpropan-2-yl group, a pentan-1-ylgroup, a pentan-2-yl group, a hexan-1-yl group, a heptan-1-yl group, anoctan-1-yl group, a nonan-1-yl group, and a decan-1-yl group. Amongthese, a linear or branched alkyl group having 1 to 8 carbon atoms ispreferred.

In a case in which R^(1d) to R^(15d) each represent a monovalent groupselected from an aromatic group, an unsaturated group, asulfur-containing group, an oxygen-containing group, aphosphorus-containing group, an alicyclic group, and a halogen atom,specific examples thereof include the groups listed as examples in thesection [Substituents] described above.

In regard to Formula (IV), at least one of R^(1d) to R^(15d) is amonovalent sulfur-containing group represented by Formula (iv-1) orFormula (iv-2). Above all, when the ease or cost of actual synthesis andheat resistance are taken into consideration, or when it is taken intoconsideration that by making the compatibility with a resin serving as amatrix satisfactory, clouding of the resin member to which the additiveof the present invention has been added can be suppressed, andmanifestation of high ultraviolet absorbency or imparting of a highrefractive index under addition of the additive in high concentrationsis enabled, it is preferable that one to three among R^(1d) to R^(15d)are monovalent sulfur-containing groups represented by Formula (iv-1) orFormula (iv-2).

The position of the monovalent sulfur-containing group represented byFormula (iv-1) or Formula (iv-2) in Formula (IV) is not particularlylimited; however, the position may be the position of R^(3d), R^(8d) orR^(13d).

The monovalent sulfur-containing group represented by Formula (iv-1) orFormula (iv-2) is incorporated into a triazine-based skeleton. Alkylgroup having 10 to 24 carbon atoms.

5. Additive Represented by Formula (V)

An additive represented by Formula (V) described above includes along-chain alkyl group in a benzotriazole-based skeleton.

In regard to Formula (V), at least one of R^(1e) to R^(9e) is an alkylgroup having 10 to 24 carbon atoms. This alkyl group having 10 to 24carbon atoms has a linear chain having 10 to 20 carbon atoms, andhydrogen atom of the linear chain may be substituted by two or feweralkyl groups each having 1 or 2 carbon atoms. Among them, a linear alkylgroup is preferred.

Specific examples of this alkyl group having 10 to 24 carbon atomsinclude a decan-1-yl group, an undecan-1-yl group, a dodecan-1-yl group,a tridecan-1-yl group, a tetradecan-1-yl group, a pentadecan-1-yl group,a hexadecan-1-yl group, a heptadecan-1-yl group, an octadecan-1-ylgroup, a nonan-1-yl group, an eicosan-1-yl group, a heneicosan-1-ylgroup, a docosan-1-yl group, a tricosan-1-yl group, and atetracosan-1-yl group.

In regard to Formula (V), in a case in which R^(1e) to R^(9e) eachrepresent a group other than the alkyl group having 10 to 24 carbonatoms as described above, R^(1e) to R^(9e) each represent a monovalentgroup selected from a hydrogen atom, a hydrocarbon group having 1 to 4carbon atoms, an aromatic group, an unsaturated group, anoxygen-containing group, a phosphorus-containing group, an alicyclicgroup, and a halogen atom.

In a case in which R^(1e) to R^(9e) each represent a monovalenthydrocarbon group, examples of this monovalent hydrocarbon group includea linear or branched alkyl group, a linear or branched alkenyl group,and a linear or branched alkynyl group. Specific examples include amethyl group, an ethan-1-yl group, a propan-1-yl group, a1-methylethan-1-yl group, a butan-1-yl group, a butan-2-yl group, a2-methylpropan-1-yl group, and a 2-methylpropan-2-yl group.

In a case in which R^(1e) to R^(9e) each represent an aromatic group, anunsaturated group, a sulfur-containing group, an oxygen-containinggroup, a phosphorus-containing group, an alicyclic group, or a halogenatom, specific examples thereof include the groups listed as examples inthe section [Substituents] described above.

In regard to Formula (V), at least one of R^(1e) to R^(9e) is the alkylgroup having 10 to 24 carbon atoms described above. Above all, when theease or cost of actual synthesis is taken into consideration, or when itis taken into consideration that by making the compatibility with aresin serving as a matrix satisfactory, clouding of the resin member towhich the additive of the present invention has been added can besuppressed, and manifestation of high ultraviolet absorbency orimparting of a high refractive index under addition of the additive inhigh concentrations is enabled, it is preferable that one or two ofR^(1e) to R^(9e) are the alkyl group having 10 to 24 carbon atomsdescribed above.

The position of the alkyl group having 10 to 24 carbon atoms describedabove in regard to Formula (V) is not particularly limited, and theposition may be the position of R^(2e) or R^(4e).

According to the present invention, in regard to the relation betweenthe fact that compatibility between an additive and a resin can beenhanced, and the melting point of the additive, the following isconsidered. In a case in which the intermolecular interaction of theadditive is strong, the interaction between the molecules of theadditive and the molecules of the resin is difficult, and compatibilitythereof is decreased. On the other hand, in a case in which theintermolecular interaction of the additive is strong, the melting pointof the additive rises. That is, the melting point of the additive servesas an index for the interaction between the molecules of the additiveand for compatibility between the additive and the resin, and it isspeculated that by incorporating a sulfur-containing group into theadditive and incorporating an appropriately selected alkyl group intothe additive, and by reducing the interaction between the molecules ofthe additive (lowering of the melting point), compatibility between theadditive and the resin can be increased.

The additives of the present invention exhibit ultraviolet absorbency bymeans of the benzotriazole-based ultraviolet absorbing skeleton or thelike, the additives cut the wavelengths in the ultraviolet region byhaving an ultraviolet absorption band in the vicinity of 250 to 400 nmwhile transmitting the wavelengths in the visible light region. There isa demand for an ultraviolet absorber that can even absorb light in theUV-A region (315 to 400 nm), which region affects photodegradation ofall organic substances. However, the additives of the present inventionhave excellent ultraviolet absorbency for the UV-A region, and dependingon the chemical structure, the additives are even capable of cuttingultraviolet ray up to a region near 400 nm. Furthermore, throughintroduction of the functional groups of Formulae (i-1,2) to (iv-1,2),the increase of the refractive index as well as the region of theultraviolet absorption band can be controlled, and the functions can beenhanced. An additive of the present invention obtained by introducing athioether group (i-2 or iv-2) into a benzotriazole group of abenzotriazole-based compound or into an a triazine-based compound,shifts significantly to a long wavelength without cutting 450 to 500 nm(visible range) and is capable of cutting ultraviolet ray in thevicinity of 360 to 400 nm, which is considered as a longer wavelengthrange even in the UV-A region. On the other hand, regarding an additiveof the present invention obtained by introducing a thioether group of(i-2) into the phenyl group on a nitrogen atom of thebenzotriazole-based compound, the absorption band shifts to a shortwavelength, and the additive may have an absorption band near 290 nm ina short wavelength region. Furthermore, an additive of the presentinvention obtained by introducing one thioether group (iv-2) into thetriazine-based compound of the present invention, has an ultravioletabsorption band in the region of short wavelength ultraviolet ray,namely, 260 to 280 nm, in addition to an ultraviolet absorption band ina long wavelength region in the vicinity of 360 to 400 nm, so that thosethe additive enables ultraviolet absorption in a wider range.

The additives of the present invention can retain transparency of resinswhen the additives are added to the resins. Also, since the additives ofthe present invention have excellent heat resistance, the additives arenot easily thermally decomposed in the course of heating, molding andprocessing a resin member containing such an additive, and therefore, aresin member that does not have impaired external appearance and inwhich the ultraviolet absorbency and high refractive indexcharacteristics are not deteriorated, is obtained. Furthermore,regarding a transparent resin member, a member having high transparencyis obtained.

A transparent resin member containing an additive of the presentinvention represented by Formula (I), in which the thioether group of(i-2) has been introduced into any one of R^(6a) to R^(9a), enablesabsorption of wavelengths in a long wavelength region while suppressingyellowing, by the benefit of peak characteristics of ultravioletabsorption in addition to the heat resistance of such an additive, thetransparency of the resin based on compatibility to the resin, and anincreased refractive index of the resin.

On the other hand, in regard to the additives of the present inventionrepresented by Formula (I) to Formula (V) having reactive functionalgroups such as a hydroxyl group, a thiol group, a carboxyl group, anamino group and a silyl group, which include polymerizable functionalgroups and crosslinkable functional groups such as a carbon-carbondouble bond, a vinyl group, a vinyloxy group, an allyl group, a(meth)acryloyl group, a maleoyl group, a styryl group and a cinnamoylgroup, in the thiol groups of (i-1) to (iv-1) and the thioether groupsof (i-2) to (iv-2), in a case in which a resin member is obtained byperforming reaction, copolymerization and molding processing using rawmaterial monomers and a resin for films and resin members containingfunctional groups (for example, an isocyanate group, an epoxy group, acarboxylic acid group, a carbonyl group, a hydroxyl group, an alkenylgroup, an alkynyl group, an ether group, a thioisocyanate group, athioepoxy group, a thiocarboxylic acid group, a thiocarbonyl group, anda thiol group) that react with those functional groups, theabove-described additives are copolymerized with those monomers or reactwith the functional groups of the resin, thereby being immobilized inthe matrix. Thus, transparency can be maintained, and the respectivefunctions of ultraviolet absorbency and increase of refractive index canbe maintained for a long period of time, without any bleed-out of theadditives.

Furthermore, as sulfur-containing groups are introduced, the refractiveindex is increased, and a high refractive index can be imparted to aresin member. The values of refractive index of the additives of thepresent invention are not particularly limited; however, the values are,for example, 1.55 or larger, preferably 1.58 to 1.62, and morepreferably in the range of 1.60 to 1.62.

The additives of the present invention have increased compatibility withresin members and can be dissolved in high concentrations such as 0.4 wt% or more, even 10 wt % or more, and particularly 30 wt % or more, whilemaintaining high transparency, by having a sulfur-containing group,particularly a sulfur-containing group having a short-chain tomedium-chain hydrocarbon as a spacer, into a benzotriazole-basedultraviolet-absorbing skeleton. Therefore, at least any one of highultraviolet absorbency and a high refractive index can be imparted whilehigh transparency is maintained. That is, dissolution in highconcentrations in a resin member in which dissolution in highconcentrations is impossible with existing ultraviolet absorbers andrefractive index enhancers is enabled, and thus, transparency as well ashigher ultraviolet absorbency or a high refractive index can be impartedto a resin member.

Above all, if an additive of the present invention has a melting pointof below 70° C. and is a liquid at normal temperature of 35° C. orlower, the additive has particularly satisfactory compatibility with aresin member. In particular, benzotriazole-based, benzophenone-based,and salicylate-based additives are such that even if the additives areadded at a high concentration of 50 wt % or more, a matrix having hightransparency is obtained.

Furthermore, imparting of ultraviolet absorbency and imparting of a highrefractive index to a matrix can be both achieved simply by adding oneadditive to one sheet of film or sheet. For example, in regard to a filmor member having a functional optical layer, such as a multilayeroptical film, it is also possible to make two layers (an ultravioletabsorbing layer and a high refractive index layer) into a single layerusing only one additive.

When the additives represented by Formula (I) to Formula (V) areproduced, reference may be made to the disclosure of the followingExamples and known technologies.

6. Resin Member Using Additive of Present Invention

A resin member of the present invention contains an additive of thepresent invention such as explained above.

The shape of the resin member of the present invention is notparticularly limited, and any arbitrary shape may be adopted. However,from the viewpoint that high ultraviolet absorbency and/or a highrefractive index can be imparted while maintaining transparency, alaminated multilayer structure can be simplified, and thus the number ofproduction processes and the production cost can be reduced. Above all,one layer in a member having a multilayer structure, a film or sheethaving softness or flexibility, or a plate-like member having aplate-sheet with rigidity is preferred, and in addition to those,optical molded articles, for example, optical lenses such as glasseslens and contact lenses, are preferred.

Resin members containing the additives of the present invention canmaintain transparency of the resins. Also, since the additives of thepresent invention have excellent heat resistance, the additives are noteasily thermally decomposed in the course of heating, molding andprocessing a resin member containing such an additive, and therefore, aresin member that does not have impaired external appearance and inwhich the ultraviolet absorbency and high refractive indexcharacteristics of the resin member are not deteriorated, is obtained.Furthermore, regarding a transparent resin member, a member having hightransparency is obtained.

Furthermore, transparent resin members containing the additives of thepresent invention represented by Formula (I) to Formula (V) in which thethioether group of (iv-2) has been introduced into R^(6a) to R^(9a),enable absorption of the wavelengths in a long wavelength region whilesuppressing yellowing, due to the transparency and increased refractiveindices of resins obtainable by the heat resistance of the thoseadditives and compatibility with the resins, as well as thecharacteristics of ultraviolet absorption peaks. In regard to resinmembers containing the additives of the present invention represented byFormula (I) to Formula (V) having reactive functional groups such as athiol group, a vinyl group and a hydroxyl group in the thiol groups of(i-1) to (iv-1) and the thioether groups of (i-2) to (iv-2), in a casein which a resin member is obtained by performing reaction and moldingprocessing using raw material monomers and a resin for films and resinmembers containing functional groups (for example, an isocyanate group,an epoxy group, a carboxylic acid group, a carbonyl group, a hydroxylgroup, an alkenyl group, an alkynyl group, an ether group, athioisocyanate group, a thioepoxy group, a thiocarboxylic acid group, athiocarbonyl group, and a thiol group) that react with the reactivefunctional groups such as a thiol group, a vinyl group and a hydroxylgroup contained in those additives, the above-described additives in theresulting resin react with the functional groups of those monomers andthe resin, thereby being immobilized in the matrix. Thus, the resin canmaintain the respective functions of ultraviolet absorbency and increaseof the refractive index for a long period of time, without any bleed-outof the additives.

A transparent resin member containing an additive of the presentinvention in which the substituent represented by Formula (i-1) orFormula (i-2) has been introduced into R^(6a) to R^(9a) of Formula (I),maintains transparency and a high refractive index, and due to thecharacteristics of ultraviolet absorbency of the additive, thetransparent resin member is capable of sharply cutting ultraviolet rayin the vicinity of 360 to 400 nm, which is considered as a longerwavelength range even in the UV-A region, without cutting thewavelengths of 450 to 500 nm (visible range). For this reason, a resinmember having suppressed yellow coloration and excellent externalappearance is obtained.

The resin member of the present invention is not particularly limited,and examples thereof include acrylic resins such as polymethyl(meth)acrylate, polyethyl (meth)acrylate, and a methyl(meth)acrylate-butyl (meth)acrylate copolymer; polyolefin-based resinssuch as polyethylene, polypropylene, polymethylpentene, and a cyclicolefin-based polymer; thermoplastic polyester resins such as apolycarbonate resin, polyethylene terephthalate, and polyethylenenaphthalate; thermoplastic resins such as polyurethane,polythiourethane, polystyrene, polyamide, polyimide, anacrylonitrile-styrene copolymer, a polyether sulfone, a polysulfone, acellulose-based resin such as triacetyl cellulose, polyvinyl acetate, anethylene-vinyl acetate copolymer, polyvinylpyrrolidone, polyvinylchloride, polyvinylidene chloride, polyether ether ketone, polyacetal,and nylon; thermosetting resins of urethane, thiourethane, urea,melamine, acrylic melamine, episulfide, epoxy, allyl, silicone, phenol,urea, and unsaturated polyesters; and ultraviolet-curable resins such asacrylics, for example, a monofunctional or polyfunctional (meth)acrylatecompound such as an acrylic acid ester of a polyhydric alcohol,2-hydroxyethyl methacrylate, or a methacrylic acid ester; apolyfunctional urethane (meth)acrylate compound synthesized from adiisocyanate and a polyhydric alcohol, or a hydroxy ester of acrylicacid or methacrylic acid; and ultraviolet-curable resins such as apolyether, a polyester, an epoxy resin, an alkyd resin, a spiroacetalresin, a polybutadiene, and a polythiol-polyene, all of which haveacrylate-based functional groups.

The resin member of the present invention can be produced by, forexample, the following methods (1) to (4), without any particularlimitations.

(1) A method of forming a film by applying a coating liquid containingan additive of the present invention and a resin or raw materialmonomers, on a base material, and subjecting the coating liquid toheating, irradiation with ultraviolet ray or drying.

(2) A method of mixing and then kneading an additive of the presentinvention with a resin or raw material monomers, and molding the mixtureand processing it into a film using an extruder or the like.

(3) A method of incorporating an additive of the present invention intoa resin adhesive, and applying the resin adhesive on a film.

(4) A method of dissolving an additive of the present invention in rawmaterial monomers, casting the solution into a mold or a glass mold,curing the raw material monomers by heating, irradiating withultraviolet radiation, or drying to thereby mold a resin.

Among these methods, the method of (1) of forming a film by applying acoating liquid containing an additive of the present invention and aresin or raw material monomer materials, is suitable for the presentinvention from the viewpoint of obtaining a transparent multilayerstructure, a film, or a sheet.

In this method, a coating liquid is produced by diluting the additive ofthe present invention and the resin or raw material monomers in anorganic solvent or a water-based solvent, or without diluting thematerials, and a film is formed by applying the coating liquid on a basematerial. If necessary, drying, cooling, heating, and irradiation withultraviolet ray are performed, and thus the film strength is increased.

The resin is not particularly limited, and for example, any film ormember having a functional optical layer can be selected as appropriate,while considering necessary properties such as adhesiveness to a basematerial and hardness. Specific examples include an ultraviolet-curableresin, an electron beam-curable resin, a thermosetting resin, and athermoplastic resin. More specific examples include a polyester resin,an acrylic resin, a urethane resin, a thiourethane resin, a polyethyleneterephthalate resin, a polystyrene resin, a polycarbonate resin, a urearesin, a melamine resin, an acrylic melamine resin, an epoxy resin, analkyd resin, a spiroacetal resin, a polybutadiene resin, a polyolefinresin, a polyvinyl resin, a polyvinyl alcohol resin, a polyvinyl-basedmodified resin (PVB, EVA and the like), a silicone resin, a polyamideresin, a polyether resin, an episulfide resin, a nylon resin, andcopolymer resins thereof.

In regard to a film or member having a functional optical layer, anultraviolet-curable resin, an electron beam-curable resin, athermosetting resin, a thermoplastic resin, and the like can be used. Acoating liquid containing these resins is applied on a transparent basematerial to form a coating film, and this coating film is subjected to adrying treatment as necessary. Subsequently, the coating film issubjected to a curing reaction by irradiating the coating film withultraviolet ray or an electron beam or heating the coating film, andthus a transparent optical layer can be formed.

Regarding the ultraviolet-curable resin, an acrylic material can beused. Examples of the acrylic material that can be used include amonofunctional or polyfunctional (meth)acrylate compound such as anacrylic acid or methacrylic acid ester; and a polyfunctional urethane(meth)acrylate compound synthesized from a diisocyanate, a polyhydricalcohol, and a hydroxy ester of acrylic acid or methacrylic acid. Inaddition to these, a polyether resin, a polyester resin, an epoxy resin,an alkyd resin, a spiroacetal resin, a polybutadiene resin, apolythiol-polyene resin and the like, all of which have acrylate-basedfunctional groups, can also be used.

In the case of using an ultraviolet-curable resin, a photopolymerizationinitiator is added to the coating liquid. The photopolymerizationinitiator may be any agent capable of generating a radical whenirradiated with ultraviolet ray. For example, an acetophenone, abenzoin, a benzophenone, a phosphine oxide, a ketal, an anthraquinone,and a thioxanthone can be used.

Examples of the thermosetting resin that can be used include a urethaneresin, a thiourethane resin, a melamine resin, an acrylic melamineresin, a urea resin, a phenolic resin, an epoxy resin, and an episulfideresin.

Examples of the thermoplastic resin that can be used include a urethaneresin, a thiourethane resin, a polyethylene terephthalate resin, apolystyrene resin, a polycarbonate resin, a polyester resin, apolyethylene resin, a polypropylene resin, an acrylic resin, and a nylonresin.

If necessary, a solvent for diluting the coating liquid may be added tothe coating liquid. Examples of the solvent include aromatichydrocarbons such as toluene, xylene, cyclohexane, andcyclohexylbenzene; hydrocarbons such as n-hexane; ethers such as dibutylether, dimethoxymethane, dimethoxyethane, diethoxyethane, propyleneoxide, dioxane, dioxolane, trioxane, tetrahydrofuran, anisole, andphenetole; ketones such as methyl isobutyl ketone, methyl butyl ketone,acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone,diisobutyl ketone, cyclopentanone, cyclohexanone, andmethylcyclohexanone; esters such as ethyl formate, propyl formate,n-pentyl formate, methyl acetate, ethyl acetate, methyl propionate,ethyl propionate, n-pentyl acetate, and γ-butyrolactone; cellosolvessuch as methyl cellosolve, cellosolve, butyl cellosolve, and cellosolveacetate; alcohols such as methanol, ethanol, and isopropyl alcohol; andwater.

If necessary, additives such as an antifoaming agent, a leveling agent,an oxidation inhibitor, a photostabilizer, a polymerization inhibitor, acatalyst, a dye, and a pigment may also be incorporated into the coatingliquid.

The amount of use of the additives of the present invention variesdepending on the purpose, and is not particularly limited inconsideration of ultraviolet absorbency, increase of refractive index,transparency and the like. However, the additives can be added in anamount of 0.4 wt % or more, even 10 wt % or more, even 30 wt % or more,and particularly 50 wt % or more, with respect to the total amount ofthe coating liquid excluding volatile components such as a solvent. Evenif the additives are added in such high concentrations, the additives ofthe present invention uniformly dissolve in a resin serving as a matrix,and thus high transparency can be maintained.

The coating liquid thus produced can be applied on a base materialaccording to an appropriate method such as bar coating, gravure coating,comma coating, lip coating, curtain coating, roll coating, bladecoating, spin coating, reverse coating, die coating, spraying, ordipping.

The base material for coating is not particularly limited; however,examples include a resin plate, a resin film, a resin sheet, a glass,and a construction material.

In a case in which the resin member of the present invention is used asa portion of a film or member having a functional optical layer such asan antireflection film, the material can be selected by taking intoconsideration of optical characteristics such as transparency and lightrefractive index, and various properties such as impact resistance, heatresistance and durability, for a base material for coating. Such amaterial is not particularly limited; however, examples include acrylicresins such as polymethyl (meth)acrylate, polyethyl (meth)acrylate, anda methyl (meth)acrylate-butyl (meth)acrylate copolymer; polyolefin-basedresins such as polyethylene, polypropylene, polymethylpentene, and acyclic olefin-based polymer; thermoplastic polyester resins such as apolycarbonate resin, polyethylene terephthalate, and polyethylenenaphthalate; thermoplastic resin materials such as polyamide, polyimide,polystyrene, an acrylonitrile-styrene copolymer, polyether sulfone,polysulfone, a cellulose-based resin such as triacetyl cellulose,polyvinyl acetate, an ethylene-vinyl acetate copolymer, polyvinylchloride, polyvinylidene chloride, polyether ether ketone, andpolyurethane; glasses (including ceramics) such as soda glass, potashglass, and lead glass; and light-transmitting inorganic materials suchas quartz, fluorite, and diamond.

To these materials, known additives, for example, an ultravioletabsorber, an infrared absorber, a refractive index enhancer, aplasticizer, a lubricating agent, a colorant, an oxidation inhibitor,and a flame retardant, may also be used.

The thickness of the base material in the case of being used as a filmhaving a functional optical layer is not particularly limited; however,the thickness is, for example, 50 nm to 150 μm. Furthermore, such a basematerial may have a single layer, or may be a laminate of a plurality oflayers.

Furthermore, among the above-described methods for producing the resinmember of the present invention, in the (2) method of mixing and thenkneading an additive of the present invention with a resin, and moldingthe mixture and processing it into a film using an extruder or the like,the resin member can be produced by adding the additive of the presentinvention to a powder or pellets of the resin, heating and melting theresin powder or pellets, and then molding the molten resin.

The powder or pellets of the resin are not particularly limited;however, examples include acrylic resins such as polymethyl(meth)acrylate, polyethyl (meth)acrylate, and a methyl(meth)acrylate-butyl (meth)acrylate copolymer; polyolefin-based resinssuch as polyethylene, polypropylene, polymethylpentene, and cyclicolefin-based polymers; thermoplastic polyester resins such as apolycarbonate resin, polyethylene terephthalate, and polyethylenenaphthalate; and thermoplastic resin materials such as polyamide,polyimide, polystyrene, an acrylonitrile-styrene copolymer, polyethersulfone, polysulfone, a cellulose-based resin such as triacetylcellulose, polyvinyl acetate, an ethylene-vinyl acetate copolymer,polyvinylpyrrolidone, polyvinyl chloride, polyvinylidene chloride,polyether ether ketone, polyacetal, nylon, and polyurethane.

The method for molding a resin member is not particularly limited;however, an injection molding method, an extrusion molding method, acalender molding method, a blow molding method, a compression moldingmethod or the like can be used. In the case of using an extruder, aresin member can be produced by producing a film using an extruder, orproducing a original sheet using an extruder, and then stretching theoriginal sheet uniaxially or biaxially to produce a film.

The additive of the present invention acquires enhanced heat resistanceby having a thioether group introduced thereinto. Since the 5% weightreduction temperature of the additive of the present invention is higherthan 100° C. to 250° C., which correspond to the softening points ofgeneral resins (“Well-Known Plastics”, reviewed by Japan PlasticsIndustry Federation, published by Nippon Jitsugyo Publishing Co., Ltd.),the additive of the present invention can be applied to thermosettingresins and thermoplastic resins having molding processing temperaturesof 100° C. to 200° C., as well as thermoplastic resins which requiremolding processing temperatures higher than 200° C. to 250° C.

When the additive and a resin are kneaded, those additives used forconventional resin molding, such as an infrared absorber, an ultravioletabsorber, a refractive index enhancer, an oxidation inhibitor, aphotostabilizer, a flame retardant, and a plasticizer may also be added.

Among the above-described methods for producing the resin member of thepresent invention, in the (3) method of incorporating an additive of thepresent invention into a resin adhesive, and applying the resin adhesiveon a film, a composite material including the resin member of thepresent invention can be produced by using known transparent adhesivesuch as a silicone-based, urethane-based, acrylic, polyvinyl butyraladhesive (PVB), ethylene-vinyl acetate-based, or epoxy-based adhesives,which are generally used as resin adhesives, adhering resin films usinga resin adhesive to which the additive of the present invention has beenadded, and curing the resin films.

The film thickness in a case in which the resin member of the presentinvention is used as a portion of a film or member having a functionaloptical layer is not particularly limited as long as the film thicknessis in a range that can satisfy required properties such as type of theresin material, adhesiveness and hardness, and the film thickness is,for example, in the range of 50 nm to 200 μm.

Furthermore, among the above-described methods for producing the resinmember of the present invention, in the (4) method of dissolving anadditive of the present invention in raw material monomers, casting thesolution into a mold or a glass mold, curing the raw material monomersby heating, irradiating with ultraviolet radiation, or drying to therebymold a resin, in the case of curing by heating, monomers forthermosetting resins can be used, and examples include, withoutparticular limitations, the resin raw material monomers capable ofproducing urethane, thiourethane, epoxy, thioepoxy, melamine, silicone,phenol, urea, and unsaturated polyester resins can be used. The additiveof the present invention is dissolved in at least one kind of monomeramong the resin raw material monomers, the other resin monomers neededfor resin production are mixed thereinto, and then the mixture is castinto a mold or a glass mold and heated. Thereby, a resin membercontaining the additive of the present invention can be produced. As anultraviolet-curable resin, an acrylic material can be used. Examples ofthe acrylic material that can be used include monofunctional orpolyfunctional (meth)acrylate compounds such as 2-hydroxyethyl acrylateor methacrylate, and a methacrylic acid ester; and a polyfunctionalurethane (meth)acrylate compound synthesized from a diisocyanate, apolyhydric alcohol, and a hydroxy ester of an acrylic acid ormethacrylic acid. In addition to these, a polyether resin, a polyesterresin, an epoxy resin, an alkyd resin, a spiroacetal resin, apolybutadiene resin, a polythiol-polyene resin and the like, all ofwhich have acrylate-based functional groups, can also be used.

The resin member of the present invention can be used in allapplications where synthetic resins are used, and without any particularlimitations, the resin member can be particularly suitably used forapplications with a possibility for exposure to light including sunlightor ultraviolet ray. Examples of the applications include coating agentsor protective agents for glass substrate (the glass substrate includingglass substitutes, window panes, lighting glass, and light sourceprotecting glass); members for light sources emitting ultraviolet ray,such as a fluorescent lamp and a mercury lamp; containers or packagingmaterials for foods and medicines; and discoloration preventing agentsfor agricultural and industrial sheets, printed matter, dyed goods, dyesand pigments, signboards, signal lamps, and cards.

Among them, the resin member of the present invention is particularlysuitable for optical material, among others, a film or member having afunctional optical layer, and an optical molded article, from theviewpoint of enabling imparting of ultraviolet absorbency or a highrefractive index while maintaining transparency of the matrix.

The film or member having a functional optical layer may be a singlelayer film, a multilayer film or an optical layer-attached substrate inwhich a single-layered or multilayered optical layer intended forvarious applications is provided on a base material film or substrate.In a case in which a multilayered optical layer is provided, the resinmember of the present invention is used in at least one of the layers.

In regard to the film or member having a functional optical layer, theoptical film may be a base material film provided with functional layersintended for various applications, and examples thereof include variousoptical disc substrate protective film, a reflective film, anantireflective film, an oriented film, a polarizing film, a polarizinglayer protective film, a retardation film, a light diffusing film, aviewing angle increasing film, an electromagnetic wave shielding film,an antiflare film, a light-shielding film, and a brightness increasingfilm.

Examples of the member having a functional optical layer include membersobtained by laminating a single layer or multiple layers of at least anyone of an antireflective layer, a hard coat layer, an antistatic layer,an adhesion stabilizing layer, a protective layer, an electromagneticwave shielding layer and an infrared cutting layer on the surface of apanel substrate or the like.

Furthermore, the resin member of the present invention is suitable for asolar cell surface protective film. A solar cell element usually has aconfiguration in which an active layer working as a solar cell isprovided between a pair of substrates; however, a flexible solar cellneeds an ultraviolet-absorbing protective film because a polyestermaterial for a gas barrier film, which is used as a member of the solarcell, or an active layer itself in an organic solar cell absorbsultraviolet ray and is deteriorated. Furthermore, since solar cells areinstalled outdoors for a long period of time, such a protective film isrequired to have high weather resistance. Furthermore, since a solarcell absorbs light energy and converts the light energy to electricpower, such a protective film is required to have high transparency.That is, a protective film for protecting a flexible solar cell isrequired to have high transparency, high ultraviolet absorbency, highweather resistance, and flexibility, and the resin member of the presentinvention is adequate for such an application.

The resin member of the present invention can be suitably used foroptical molded articles such as lens elements for glasses lens plastics;optical lenses such as contact lenses, optical pickup lenses, cameralenses, and lenticular lenses; optical substrates such as prisms,filters, substrates for touch panels, and light-guiding plates; opticalfibers, and optical molded articles such as information recording media.Regarding optical lenses, the resin member of the present invention isalso suitable for plastic lenses such as lens films such as a Fresnelscreen film and a lenticular lens film; or a microlens array usingmicrolenses having a several micrometer-sized minute diameter, which areused for the purpose of increasing light collecting properties or lightdiffusibility in miniaturized optical functional elements, or for thepurpose of collecting light in an image-capturing element or alight-receiving element.

Furthermore, the resin member of the present invention is also suitablefor display substrates, for example, substrates for flat panel displayssuch as liquid crystal displays, organic EL displays, plasma displays,field emission displays, and electronic papers; and substrates forbacklights of liquid crystal displays, signals, and neon signs.

In a case in which ultraviolet ray having wavelengths in a wide range isabsorbed by a resin member such as a film, it is necessary to usemultiple additives, to add an additive at a high concentration, or tomake the film or resin thicker. However, in this case, it is likely tohave problems in view of transparency and coloration. However, atriazine-based compound obtained by introducing one thioether group,which is used as an additive of the present invention, has anultraviolet absorption band in a long wavelength region of 360 to 400 nmand in a short wavelength ultraviolet region of 260 to 280 nm, andenables ultraviolet absorption in a wider range. Thus, ultraviolet rayhaving wavelengths in a wide range can be absorbed by a single additivein low concentrations.

For example, it is desirable for a light-shielding film to be capable ofcutting ultraviolet ray up to 360 to 400 nm; however, general additivescut light up to 450 to 500 nm (visible range) and thereby have a problemof attenuating visible light or being discolored. However, an additiveof the present invention obtained by introducing a thioether group (i-2,iv-2) into a benzotriazole group of a benzotriazole-based compound orinto a triazine-based compound, is capable of cutting ultraviolet rayhaving a longer wavelength of 360 to 400 nm even in the range of 315 to400 nm (UV-A region), without cutting 450 to 500 nm (visible range).Thus, the additive of the present invention is highly useful.

The additive of the present invention that is obtained by introducing athioether group of (i-2) into the phenyl group on a nitrogen atom of abenzotriazole-based compound, and has an ultraviolet absorption peak topnear 290 nm in a short wavelength region, can efficiently preventdeterioration in, for example, a resin that is deteriorated atwavelengths in the vicinity of 290 to 300 nm, such as polyethylene,polymethyl methacrylate, or polycarbonate.

Furthermore, the additives of the present invention can be used not onlyin films and resin members but also in, for example, dyes, pigments,coloring materials, inks, paints, pharmaceutical products, surfacecoatings, cosmetics, photographic materials, and fabrics, which arerequired to be stabilized and functionalized by ultraviolet absorberswhile having the above-described functions.

EXAMPLES

Hereinafter, the present invention will be described in more detail byway of Examples; however, the present invention is not intended to belimited to these Examples.

<Synthesis Example 1> Synthesis of Intermediate 1

Dibromohexane (50.0 g, 204.9 mmol) and S-potassium thioacetate (10.6 g,102.5 mmol) were heated to reflux for 6 hours in 150 mL of acetonitrile.After completion of the reaction, a solid thus produced was separated byfiltration, and the solvent was distilled off from the filtrate. Thus, aliquid crude product was obtained. Then, the crude product was purifiedusing a column, and thereby Intermediate 1 was obtained as a transparentliquid.

<Synthesis Example 2> Synthesis of Intermediate 2

Dibromodecane (50.0 g, 166.6 mmol) and S-potassium thioacetate (8.6 g,83.3 mmol) were heated to reflux for 6 hours in 150 mL of acetonitrile.After completion of the reaction, a solid thus produced was separated byfiltration, and the solvent was distilled off from the filtrate. Thus, aliquid crude product was obtained. Then, the crude product was purifiedusing a column, and thereby Intermediate 2 was obtained as a transparentliquid.

<Synthesis Example 3> Synthesis of Intermediate 3

Br(CH₂)₃S(CH₂)₇CH₃  (Intermediate 3)

Octanethiol (29.3 g, 200 mmol) and 55% sodium hydride (13.1 g, 300 mmol)were stirred in 150 ml of THF for 2 hours under ice cooling, and then asuspension solution thus obtained was added dropwise to 100 mL of a THFsolution of dibromopropane (121.1 g, 600 mmol) under ice cooling. Themixture was allowed to react for 2 hours. Toluene was added thereto, themixture was washed with water, and then the resultant was subjected todistillation under reduced pressure. Thus, Intermediate 3 was obtained.

<Synthesis Example 4> Synthesis of Intermediate 4

HS(CH₂)₃S(CH₂)₇CH₃  (Intermediate 4)

Intermediate 3 (7.5 g, 28.2 mmol) and S-potassium thioacetate (3.4 g,29.6 mmol) were heated to reflux for 6 hours in 100 mL of acetonitrile.After completion of the reaction, a solid thus produced was separated byfiltration, and the solvent was distilled off from the filtrate. Thus, aliquid compound was obtained. The compound thus obtained and an ethanol(100 mL) solution of sodium hydroxide (2.2 g, 55.6 mmol) were heated toreflux for 6 hours, and then the mixture was cooled to room temperatureand was acidified using hydrochloric acid. Toluene was added to thereaction liquid, and the mixture was subjected to washing with water,solvent distillation, and purification with a column. Thus, Intermediate4 was obtained as a liquid.

<Synthesis Example 5> Synthesis of Intermediate 5

Hydroxybenzenethiol (10.0 g, 79.2 mmol), iodomethane (10.7 g, 75.2mmol), and potassium carbonate (13.4 g, 96.9 mmol) were heated to refluxfor 6 hours in 150 mL of acetonitrile. After completion of the reaction,toluene was added to the reaction liquid, and the mixture was subjectedto washing with water, distillation of the solvent, and purificationusing a column. Thus, Intermediate 5 was obtained as a liquid.

<Synthesis Example 6> Synthesis of Intermediate 6

Hydroxybenzenethiol (15.0 g, 118.8 mmol), bromohexane (18.63 g, 112.8mmol), and potassium carbonate (24.6 g, 178.2 mmol) were heated toreflux for 6 hours in 150 mL of acetonitrile. After completion of thereaction, toluene was added to the reaction liquid, and the mixture wassubjected to washing with water, distillation of the solvent, andpurification using a column. Thus, Intermediate 6 was obtained as aliquid.

<Synthesis Example 7> Synthesis of Intermediate 7

Hydroxybenzenethiol (10.0 g, 79.2 mmol), bromooctane (14.6 g, 75.6mmol), and potassium carbonate (13.4 g, 96.9 mmol) were heated to refluxfor 6 hours in 150 mL of acetonitrile. After completion of the reaction,toluene was added to the reaction liquid, and the mixture was subjectedto washing with water, distillation of the solvent, and purificationusing a column. Thus, Intermediate 7 was obtained as a liquid.

<Synthesis Example 8> Synthesis of Intermediate 8

Hydroxybenzenethiol (10.0 g, 79.2 mmol), Intermediate 3 (20.2 g, 75.6mmol), and potassium carbonate (13.4 g, 96.9 mmol) were heated to refluxfor 6 hours in 150 mL of acetonitrile. After completion of the reaction,toluene was added to the reaction liquid, and the mixture was subjectedto washing with water, distillation of the solvent, and purificationusing a column. Thus, Intermediate 8 was obtained as a liquid.

<Synthesis Example 9> Synthesis of Compound 1

2-(2-Hydroxy-5-methylphenyl)benzotriazole (10.0 g, 44.4 mmol),Intermediate 1 (11.6 g, 48.8 mmol), and potassium carbonate (12.3 g,88.8 mmol) were heated to reflux for 6 hours in 100 mL of acetonitrile.After completion of the reaction, toluene was added to the reactionliquid, and the mixture was subjected to washing with water,distillation of the solvent, and purification using a column. Thus,Intermediate 9 as described below was obtained as a liquid.

Intermediate 9 (5.0 g, 13.1 mmol) and an ethanol (100 mL) solution ofsodium hydroxide (1.0 g, 26.1 mmol) were heated to reflux for 6 hours,and then the mixture was cooled to room temperature and was acidifiedusing hydrochloric acid. Toluene was added to the reaction liquid, andthe mixture was subjected to washing with water, distillation of thesolvent, and purification using a column. Thus, Compound 1 was obtainedas a liquid.

FT-IR (KBr): 2550 cm⁻¹: S—H stretching vibration, 1464, 1403 cm⁻¹:triazole ring stretching vibration, 1073 cm⁻¹: —O—CH₂ antisymmetricstretching vibration

¹H-NMR (CDCl₃ 400 MHz): δ1.24 (m, 5H, O—(CH₂)₂CH ₂CH ₂(CH₂)₂—SH), 1.43(m, 2H, O—(CH₂)₄CH ₂CH₂—SH), 1.63 (m, 2H, O—CH₂CH ₂(CH₂)₄—SH), 2.34 (m,5H, O—(CH₂)₅CH ₂—SH, -Ph-CH ₃—O—), 3.99 (tri, 2H, O—CH ₂(CH₂)₅—SH), 7.00(d, 1H), 7.24 (d, 1H), 7.42 (m, 2H), 7.47 (s, 1H), 7.97 (m, 2H)(insg.7arom. CH)

¹³C-NMR (CDCl₃ 400 MHz): δ20.0 (C_(arom)—CH₃), 24.4 (O—(CH₂)₅ CH₂—SH),25.4 (O—(CH₂)₂ CH₂(CH₂)₃—SH), 27.8 (O—(CH₂)₃ CH₂(CH₂)₂—SH), 28.8 (O—CH₂CH₂(CH₂)₄—SH), 33.8 (O—(CH₂)₄ CH₂CH₂—SH), 69.6 (O—CH₂(CH₂)₅—SH), 117.6,127.7, 129.6, 131.5 (CH_(arom)), 114.5, 147.5 ({right arrow over(C)}_(arom)), 130.5 ({right arrow over (C)}_(arom)—CH₃), 151.0 (C_(arom)O—)

<Synthesis Example 10> Synthesis of Compound 2

Compound 2 was synthesized by a synthesis method similar to that usedfor Compound 1, using Intermediate 2 (14.3 g, 48.8 mmol). The propertiesvalues are shown below.

FT-IR (KBr): 2559 cm⁻¹: S—H stretching vibration, 1465, 1403 cm⁻¹:triazole ring stretching vibration, 1073 cm⁻¹: —O—CH₂ antisymmetricstretching vibration

¹H-NMR (CDCl₃ 400 MHz): δ 1.18 (m, 10H, O—(CH₂)₃(CH ₂)₅(CH₂)₂—SH), 1.32(m, 3H, O—(CH₂)₂CH ₂ (CH₂)₇—SH), 1.60 (m, 4H, O—CH₂CH ₂(CH₂)₆CH ₂CH₂SH),2.37 (s, 3H, -Ph-CH ₃—O—), 2.50 (quin, 2H, O—(CH₂)₉CH ₂SH), 4.00 (tri,2H, O—CH ₂(CH₂)₉SH), 7.03 (d, 1H), 7.25 (d, 1H), 7.42 (m, 2H), 7.47 (s,1H), 7.97 (m, 2H) (insg.7arom. CH)

¹³C-NMR (CDCl₃ 400 MHz): δ20.0 (C_(arom)—CH₃), 24.6 (O—(CH₂)₉ CH₂—SH),25.7 (O—(CH₂)₂ CH₂(CH₂)₇—SH), 28.3 (O—(CH₂)₃ CH₂(CH₂)₆—SH), 28.9(O—(CH₂)₄ CH₂(CH₂)₅—SH), 29.0 (O—(CH₂)₅ CH₂(CH₂)₄—SH), 29.1 (O—(CH₂)₆CH₂(CH₂)₃—SH), 29.2 (O—(CH₂)₇ CH₂(CH₂)₂—SH), 29.4 (O—(CH₂)₈ CH₂CH₂—SH),34.0 (O—CH₂ CH₂(CH₂)₈—SH), 69.6 (O—CH₂(CH₂)₉—SH), 117.6, 127.7, 129.6,131.5 (CH_(arom)), 114.5, 147.5 (C _(arom)), 130.5 (C _(arom)—CH₃),151.0 (C _(arom)O—)

<Synthesis Example 11> Synthesis of Compound 3

Concentrated hydrochloric acid (11 ml, 0.13 mol) was added to an aqueoussolution (100 mL) of nitroaniline (2.64 g, 19.1 mmol), and then anaqueous solution (15 mL) of sodium nitrite (2.64 g, 19.1 mmol) was addeddropwise thereto for 30 minutes under ice cooling. The mixture wasallowed to react for 30 minutes, and thereby a diazonium salt of anintermediate was obtained. Next, an aqueous solution of theaforementioned diazonium salt was added dropwise to an aqueous solution(150 mL) obtained by mixing Intermediate 7 (5.0 g, 20.1 mmol) withsodium hydroxide (0.96 g, 23.9 mmol) for one hour under ice cooling, andthe mixture was allowed to react for one hour. After completion of thereaction, the reaction mixture was acidified with hydrochloric acid,toluene was added thereto, and the mixture was washed with water.Subsequently, the solvent was distilled off, and the residue wassubjected to recrystallization. Thus, Intermediate 10 as described belowwas obtained.

Intermediate 10 (4.50 g, 9.7 mmol), a 1.2% aqueous solution of hydrazine(50 ml), and sodium hydroxide (1.73 g, 34.13 mmol) were reacted for 12hours in toluene (100 mL) while the mixture was heated to reflux. Thereaction mixture was cooled to room temperature, subsequently thereaction mixture was washed with water, and the solvent was distilledoff. Thus, a liquid intermediate was obtained. That intermediate,concentrated sulfuric acid (0.78 mL), and zinc (3.04 g, 46.5 mmol) werereacted for 12 hours in toluene (100 mL), while the mixture was heatedto reflux. Subsequently, the reaction liquid was subjected to washingwith water, distillation of the solvent, and purification using acolumn, and thus Compound 3 was obtained as a liquid.

FT-IR (KBr): 3270 cm⁻¹: O—H stretching vibration, 1437, 1411 cm⁻¹:triazole ring stretching vibration, 660 cm⁻¹: C—S stretching vibration

¹H-NMR (CDCl₃ 400 MHz): δ 0.83 (t, 3H, CH ₃(CH₂)₇—S), 1.27 (m, 10H,CH₃(CH ₂)₅ (CH₂)₂—S), 1.54 (quin, 2H, CH₃(CH₂)₅CH ₂CH₂—S), 2.79 (t, 2H,CH₃(CH₂)₆CH ₂—S), 6.40 (s, 1H, Ph-OH), 6.70 (d, 1H), 6.91 (s, 1H), 7.46(m, 2H), 7.51 (d, 1H), 7.98 (m, 2H) (insg.7arom. CH)

¹³C-NMR (CDCl₃ 400 MHz): δ 13.0 (CH₃(CH₂)₇—S), 21.6 (CH₃ CH₂(CH₂)₆—S),28.0 (CH₃CH₂ (CH₂)₄(CH₂)₂—S), 30.7 (CH₃(CH₂)₅ CH₂CH₂—S), 32.0(CH₃(CH₂)₅CH₂ CH₂—S), 111.6, 113.6, 117.3, 126.1, 126.9, 135.4(CH_(arom)), 131.3 (C _(arom)—S), 143.5 (C _(arom)), 156.4 (C _(arom)OH)

<Synthesis Example 12> Synthesis of Compound 4

Compound 4 was synthesized by a synthesis method similar to that usedfor Compound 3, using Intermediate 8 (5.7 g, 20.1 mmol). The propertiesvalues are shown below.

FT-IR (KBr): 3059 cm⁻¹: O—H stretching vibration, 1437, 1399 cm⁻¹:triazole ring stretching vibration, 669 cm⁻¹: C—S stretching vibration

¹H-NMR (CDCl₃ 400 MHz): δ 0.87 (t, 3H, CH ₃(CH₂)₇—S), 1.25 (m, 10H,CH₃(CH ₂)₅(CH₂)₂—S), 1.53 (quin, 2H, CH₃(CH₂)₅CH ₂CH₂—S), 1.86 (quin,2H, S—CH₂CH ₂CH₂—S-Ph), 2.43 (t, 2H, CH₃(CH₂)₆CH ₂—S), 2.54 (t, 2H, S—CH₂CH₂CH₂—S-Ph), 2.96 (t, 2H, S—CH₂CH₂CH ₂—S-Ph), 5.95 (s, 1H, Ph-OH),6.74 (d, 1H), 6.97 (s, 1H), 7.44 (m, 2H), 7.57 (d, 1H), 7.98 (m, 2H)(insg.7arom. CH)

¹³C-NMR (CDCl₃ 400 MHz): δ14.1 (CH₃(CH₂)₇—S), 22.6 (CH₃ CH₂(CH₂)₆—S),28.2 (CH₃(CH₂)₂ CH₂(CH₂)₄—S), 28.9 (CH₃(CH₂)₅ CH₂CH₂—S), 29.2 (CH₃(CH₂)₃CH₂ CH₂(CH₂)₂—S), 29.6 (CH₃(CH₂)₆ CH₂—S), 30.9 (S—CH₂ CH₂CH₂—S), 31.8(CH₃ CH₂CH₂(CH₂)₅—S), 32.1 (S—CH₂CH₂ CH₂—S), 112.9, 114.8, 118.4, 128.0,135.7 (C _(arom)H), 127.0 (C _(arom)—N), 144.6 (C _(arom)), 134.1 (C_(arom)—S), 156.9 (C _(arom)—OH)

<Synthesis Example 13> Synthesis of Compound 6

2-(2-Hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (60.0 g,0.190 mol), butanethiol (34.3 g, 0.380 mol), potassium carbonate (57.8g, 0.418 mol), and potassium iodide (2.21 g, 0.013 mol) were allowed toreact for 12 hours at 125° C. in 150 g of DMF. After completion of thereaction, the pH was adjusted, subsequently the reaction liquid wassubjected to filtration, washing with MeOH, and washing with water, andrecrystallization was performed. Thus, Compound 6 was obtained.

FT-IR (KBr): 3000 cm⁻¹: O—H stretching vibration, 1445, 1392 cm⁻¹:triazole ring stretching vibration, 661 cm⁻¹: C—S stretching vibration

¹H-NMR (CDCl₃ 400 MHz): δ 0.96 (t, 3H, CH ₃(CH₂)₃—S), 1.49 (m, 11H,-Ph-OH—CH₃—C(CH ₃)₃, CH₃CH ₂CH₂CH₂—S), 1.75 (quin, 2H, CH₃CH₂CH ₂CH₂—S),2.38 (s, 3H, -Ph-OH—CH ₃—C(CH₃)₃), 3.03 (t, 2H, CH₃CH₂CH₂CH ₂—S), 7.16(s, 1H), 7.37 (d, 1H), 7.70 (s, 1H), 7.81 (d, 1H), 8.05 (d, 1H),(insg.5arom. CH), 11.61 (s, 1H, -Ph-OH—CH₃—C(CH₃)₃)

¹³C-NMR (CDCl₃ 400 MHz): δ 13.7 (CH₃(CH₂)₃—S), 20.9(-Ph-OH—CH₃—C(CH₃)₃), 22.1 (CH₃ CH₂CH₂CH₂—S), 29.5 (-Ph-OH—CH₃—C(CH₃)₃),30.8 (-Ph-OH—CH₃—C(CH₃)₃), 32.8 (CH₃CH₂ CH₂CH₂—S), 35.4 (CH₃CH₂CH₂CH₂—S), 113.6, 117.5, 119.3, 128.7, 129.3 (CH_(arom)), 125.4, 141.2,143.4 (C _(arom)), 128.3 (C _(arom)—CH₃), 138.0 (C _(arom)—S), 139.1 (C_(arom)—C(CH₃)₃), 146.7 (C _(arom)—OH)

<Synthesis Example 14> Synthesis of Compound 7

2-(2-Hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (50.0 g,0.158 mol), hexanethiol (37.4 g, 0.316 mol), potassium carbonate (48.1g, 0.348 mol), and potassium iodide (1.8 g, 0.011 mol) were allowed toreact for 12 hours at 125° C. in 125 g of DMF. After completion of thereaction, the pH was adjusted, subsequently the reaction liquid wassubjected to filtration, washing with MeOH, and washing with water, andrecrystallization was performed. Thus, Compound 7 was obtained.

FT-IR (KBr): 2956 cm⁻¹: O—H stretching vibration, 1445, 1392 cm⁻¹:triazole ring stretching vibration, 662 cm⁻¹: C—S stretching vibration

¹H-NMR (CDCl₃ 400 MHz): δ 0.89 (t, 3H, CH ₃(CH₂)₅—S), 1.33 (m, 4H,CH₃(CH ₂)₂(CH₂)₃—S), 1.49 (m, 11H, -Ph-OH—CH₃—C(CH ₃)₃, CH₃(CH₂)₂CH₂(CH₂)₂—S), 1.73 (quin, 2H, CH₃(CH₂)₃CH ₂CH₂—S), 2.38 (s, 3H, -Ph-OH—CH₃—C(CH₃)₃), 3.02 (t, 2H, CH₃(CH₂)₃CH₂CH ₂—S), 7.16 (s, 1H), 7.36 (d,1H), 7.69 (s, 1H), 7.78 (d, 1H), 8.04 (s, 1H), (insg.5arom. CH), 11.62(s, 1H, -Ph-OH—CH₃—C(CH₃)₃)

¹³C-NMR (CDCl₃ 400 MHz): δ 14.0 (CH₃(CH₂)₅—S), 20.9(-Ph-OH—CH₃—C(CH₃)₃), 22.6 (CH₃ CH₂(CH₂)₃CH₂—S), 28.7(CH₃CH₂(CH₂)₂CH₂CH₂—S), 29.5 (-Ph-OH—CH₃—C(CH₃)₃), 31.8(-Ph-OH—CH₃—C(CH₃)₃), 33.8 (CH₃(CH₂)₃ CH₂CH₂—S), 35.4 (CH₃(CH₂)₃CH₂CH₂—S), 113.6, 117.5, 119.3, 128.7, 129.2 (CH_(arom)), 125.4, 141.2,143.4 (C _(arom)), 128.3 (C _(arom)—CH₃), 138.0 (C _(arom)—S), 139.1 (C_(arom)—C(CH₃)₃), 146.7 (C _(arom)—OH)

<Synthesis Example 15> Synthesis of Compound 8

2-(2-Hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (5.00 g,15.8 mmol), octanethiol (7.63 g, 52.1 mmol), potassium carbonate (7.20g, 52.1 mmol), and potassium iodide (0.18 g, 1.1 mmol) were allowed toreact for 20 hours at 150° C. in 50 m of DMF. After completion of thereaction, toluene was added thereto, and the mixture was subjected towashing with water, distillation of the solvent, and purification usinga column. Thus, Compound 8 was obtained.

FT-IR (KBr): 3125 cm⁻¹: O—H stretching vibration, 1438, 1391 cm⁻¹:triazole ring stretching vibration, 661 cm⁻¹: C—S stretching vibration

¹H-NMR (CDCl₃ 400 MHz): δ 0.88 (t, 3H, CH ₃(CH₂)₇—S), 1.27 (m, 8H,CH₃(CH ₂)₄(CH₂)₃—S), 1.49 (m, 11H, -Ph-OH—CH₃—C(CH ₃)₃, CH₃(CH₂)₄CH₂(CH₂)₂—S), 1.75 (quin, 2H, CH₃(CH₂)₅CH ₂CH₂—S), 2.38 (s, 3H, -Ph-OH—CH₃—C(CH₃)₃), 3.03 (t, 2H, CH₃(CH₂)₅CH₂CH ₂—S), 7.16 (s, 1H), 7.37 (d,1H), 7.70 (s, 1H), 7.81 (d, 1H), 8.05 (s, 1H), (insg.5arom. CH), 11.61(s, 1H, -Ph-OH—CH₃—C(CH₃)₃)

¹³C-NMR (CDCl₃ 400 MHz): δ 14.0 (CH₃(CH₂)₇—S), 20.0 (-Ph-OH—CH₃—C(CH₃)₃), 22.6 (-Ph-OH—CH₃—C(CH₃)₃), 28.7 (CH₃(CH₂)₅CH₂CH₂—S), 31.9(-Ph-OH—CH₃—C(CH₃)₃), 33.2 (CH₃(CH₂)₅ CH₂CH₂—S), 35.4 (CH₃(CH₂)₅CH₂CH₂—S), 113.6, 117.5, 119.3, 128.7, 129.3 (CH_(arom)), 141.2, 143.4 (C_(arom)), 125.4 (C _(arom)—N), 128.3 (C_(arom)—CH₃), 138.0 (C_(arom)—S), 139.1 (C _(arom)—C(CH₃)₃), 146.7 (C _(arom)—OH)

<Synthesis Example 16> Synthesis of Compound 9

2-(2-Hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (50.0 g,0.158 mol), decanol (55.2 g, 0.317 mol), potassium carbonate (48.1 g,0.348 mol), and potassium iodide (1.8 g, 0.011 mol) were allowed toreact for 12 hours at 125° C. in 125 g of DMF. After completion of thereaction, the pH was adjusted, subsequently the reaction liquid wassubjected to filtration, washing with MeOH, and washing with water, andrecrystallization was performed. Thus, Compound 9 was obtained.

FT-IR (KBr): 2958 cm⁻¹: O—H stretching vibration, 1448, 1392 cm⁻¹:triazole ring stretching vibration, 641 cm⁻¹: C—S stretching vibration

¹H-NMR (CDCl₃ 400 MHz): δ 0.89 (t, 3H, CH ₃(CH₂)₉—S), 1.26 (m, 12H,CH₃(CH ₂)₆(CH₂)₃—S), 1.49 (m, 11H, -Ph-OH—CH₃—C(CH ₃)₃, CH₃(CH₂)₆CH₂(CH₂)₂—S), 1.74 (quin, 2H, CH₃(CH₂)₇CH ₂CH₂—S), 2.38 (s, 3H, -Ph-OH—CH₃—C(CH₃)₃), 3.03 (t, 2H, CH₃(CH₂)₇CH₂CH ₂—S), 7.16 (s, 1H), 7.36 (d,1H), 7.69 (s, 1H), 7.78 (d, 1H), 8.05 (s, 1H), (insg.5arom. CH), 11.62(s, 1H, -Ph-OH—CH₃—C(CH₃)₃)

¹³C-NMR (CDCl₃ 400 MHz): δ 14.0 (CH₃(CH₂)₉—S), 20.9(-Ph-OH—CH₃—C(CH₃)₃), 22.7 (CH₃ CH₂(CH₂)₇CH₂—S), 28.7˜29.5 (CH₃CH₂(CH₂)₆CH₂CH₂—S), 29.6 (-Ph-OH—CH₃—C(CH₃)₃), 31.9 (-Ph-OH—CH₃—C(CH₃)₃),33.1 (CH₃(CH₂)₇ CH₂CH₂—S), 35.4 (CH₃(CH₂)₇CH₂ CH₂—S), 113.6, 117.5,119.3, 128.7, 129.3 (CH_(arom)), 125.4, 141.2, 143.4 (C _(arom)), 128.3(C _(arom)—CH₃), 138.0 (C _(arom)—S), 139.1 (C _(arom)—C(CH₃)₃), 146.7(C _(arom)—OH)

<Synthesis Example 17> Synthesis of Compound 10

Compound 10 was synthesized by a synthesis method similar to that usedfor Compound 8, using dodecanethiol (10.5 g, 52.1 mmol) instead ofoctanethiol. The properties values are shown below.

FT-IR (KBr): 3009 cm⁻¹: O—H stretching vibration, 1441, 1390 cm⁻¹:triazole ring stretching vibration, 662 cm⁻¹: C—S stretching vibration

¹H-NMR (CDCl₃ 400 MHz): δ 0.88 (t, 3H, CH ₃(CH₂)₁₁—S), 1.25 (m, 16H,CH₃(CH ₂)₈(CH₂)₃—S), 1.49 (m, 11H, -Ph-OH—CH₃—C(CH ₃)₃, CH₃(CH₂)₈CH₂(CH₂)₂—S), 1.74 (quin, 2H, CH₃(CH₂)₉CH ₂CH₂—S), 2.38 (s, 3H, -Ph-OH—CH₃—C(CH₃)₃), 3.03 (t, 2H, CH₃(CH₂)₁₀CH ₂—S), 7.16 (s, 1H), 7.37 (d, 1H),7.70 (s, 1H), 7.81 (d, 1H), 8.05 (s, 1H) (insg.5arom. CH), 11.61 (s, 1H,-Ph-OH—CH₃—C(CH₃)₃)

¹³C-NMR (CDCl₃ 400 MHz): δ 14.0 (CH₃(CH₂)₁₁—S), 20.9(-Ph-OH—CH₃—C(CH₃)₃), 22.7 (-Ph-OH—CH₃—C(CH₃)₃), 28.7˜29.7(CH₃(CH₂)₉CH₂CH₂—S), 31.9 (-Ph-OH—CH₃—C(CH₃)₃), 33.2 (CH₃(CH₂)₉CH₂CH₂—S), 35.4 (CH₃(CH₂)₉CH₂ CH₂—S), 113.5, 117.5, 119.3, 128.6, 129.3(CH_(arom)), 141.2, 143.4 (C _(arom)), 125.4 (C _(arom)—N), 128.3(C_(arom)—CH₃), 138.0 (C _(arom)—S), 139.1 (C _(arom)—C(CH₃)₃), 146.7 (C_(arom)—OH)

<Synthesis Example 18> Synthesis of Compound 11

Compound 11 was synthesized by a synthesis method similar to that usedfor Compound 8, using octadecanethiol (14.9 g, 52.1 mmol) instead ofoctanethiol. The properties values are shown below.

FT-IR (KBr): 3059 cm⁻¹: O—H stretching vibration, 1445, 1391 cm⁻¹:triazole ring stretching vibration, 664 cm⁻¹: C—S stretching vibration

¹H-NMR (CDCl₃ 400 MHz): δ 0.88 (t, 3H, CH ₃(CH₂)₁₇—S), 1.25 (m, 30H,CH₃(CH ₂)₁₅(CH₂)₂—S), 1.49 (s, 9H, -Ph-OH—CH₃—C(CH ₃)₃, 1.74 (quin, 2H,CH₃(CH₂)₁₅CH ₂CH₂—S), 2.38 (s, 3H, -Ph-OH—CH ₃—C(CH₃)₃), 3.03 (t, 2H,CH₃(CH₂)₁₅CH₂CH ₂—S), 7.16 (s, 1H), 7.37 (d, 1H), 7.70 (s, 1H), 7.81 (d,1H), 8.05 (s, 1H) (insg.5arom. CH), 11.61 (s, 1H, -Ph-OH—CH₃—C(CH₃)₃)

¹³C-NMR (CDCl₃ 400 MHz): δ 13.1 (CH₃(CH₂)₁₇—S), 19.9(-Ph-OH—CH₃—C(CH₃)₃), 21.6 (-Ph-OH—CH₃—C(CH₃)₃), 28.5 (CH₃(CH₂)₁₆CH₂—S),30.6 (C_(arom)-(-Ph-OH—CH₃—C(CH₃)₃), 34.4 (CH₃(CH₂)₁₆ CH₂—S), 115.5,117.6, 118.2, 127.2, 128.0 (CH_(arom)), 141.9, 142.9 (C _(arom)), 124.2(C _(arom)—N), 128.1 (C_(arom)—CH₃), 132.3 (C _(arom)—S), 140.0 (C_(arom)—C(CH₃)₃), 145.6 (C _(arom)—OH)

<Synthesis Example 19> Synthesis of Compound 12

2-(3,5-Di-tert-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole (25.0 g,69.85 mmol), butanethiol (20.43 g, 139.71 mmol), potassium carbonate(21.23 g, 153.68 mmol), and potassium iodide (2.21 g, 4.82 mmol) wereallowed to react for 12 hours at 125° C. in 150 g of DMF. Aftercompletion of the reaction, the pH was adjusted, and then the reactionliquid was subjected to filtration and washing with MeOH. Subsequently,the pH was adjusted again, the resultant was washed with water, andrecrystallization was performed. Thus, Compound 12 was obtained.

FT-IR (KBr): 2953 cm⁻¹: O—H stretching vibration, 1439, 1392 cm⁻¹:triazole ring stretching vibration, 667 cm⁻¹: C—S stretching vibration

¹H-NMR (CDCl₃ 400 MHz): δ 0.88 (t, 3H, CH ₃(CH₂)₇—S), 1.27 (m, 8H, CH₃(CH ₂)₄(CH₂)₃—S), 1.39 (s, 9H, -Ph-OH—C(CH ₃)₃—C(CH₃)₃), 1.51 (m, 11H,-Ph-OH—C(CH₃)₃—C(CH ₃)₃, CH₃(CH₂)₂CH ₂(CH₂)₂—S), 1.75 (quin, 2H,CH₃(CH₂)₅CH ₂CH₂—S), 3.03 (t, 2H, CH₃(CH₂)₅CH₂CH ₂—S), 7.37 (d, 1H),7.40 (s, 1H), 7.71 (s, 1H), 7.82 (d, 1H), 8.24 (d, 1H), (insg.5arom.CH), 11.66 (s, 1H, -Ph-OH—C(CH₃)₃—C(CH₃)₃)

¹³C-NMR (CDCl₃ 400 MHz): δ 14.1 (CH₃(CH₂)₇—S), 22.6 (CH₃ CH₂(CH₂)₆—S),28.7˜29.2 (CH₃CH₂ (CH₂)₄CH₂CH₂—S), 29.6 (-Ph-OH—C(CH₃)₃—C(CH₃)₃), 31.5(-Ph-OH—C(CH₃)₃—C(CH₃)₃), 31.8 (CH₃CH₂(CH₂)₄ CH₂CH₂—S), 33.2(-Ph-OH—C(CH₃)₃—C(CH₃)₃), 34.6 (CH₃(CH₂)₄CH₂ CH₂—S), 35.7(-Ph-OH—C(CH₃)₃—C(CH₃)₃), 113.6, 116.0, 117.6, 129.2, 143.4 (CH_(arom)),125.0, 141.2, 143.4 (C _(arom)), 137.9 (C _(arom)—S), 125.2, 138.6 (C_(arom)—C(CH₃)₃), 146.6 (C _(arom)—OH)

<Synthesis Example 20> Synthesis of Compound 13

2-(3,5-DI-tert-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole (25.0 g,69.85 mmol), dodecanethiol (28.28 g, 139.72 mmol), potassium carbonate(21.24 g, 153.68 mmol), and potassium iodide (0.81 g, 4.88 mmol) wereallowed to react for 12 hours at 125° C. in 62.5 g of DMF. Aftercompletion of the reaction, the pH was adjusted, and then the reactionliquid was subjected to filtration and washing with MeOH. Subsequently,the pH was adjusted again, the resultant was washed with water, andrecrystallization was performed. Thus, Compound 13 was obtained.

FT-IR (KBr): 2962 cm⁻¹: O—H stretching vibration, 1434, 1389 cm⁻¹:triazole ring stretching vibration, 668 cm⁻¹: C—S stretching vibration

¹H-NMR (CDCl₃ 400 MHz): δ 0.87 (t, 3H, CH ₃(CH₂)₁₁—S), 1.26 (m, 16H,CH₃(CH ₂)₈(CH₂)₃—S), 1.39 (s, 9H, -Ph-OH—C(CH ₃)₃—C(CH₃)₃), 1.51 (m,11H, -Ph-OH—C(CH₃)₃—C(CH ₃)₃, CH₃(CH₂)₈CH ₂(CH₂)₂—S), 1.74 (quin, 2H,CH₃(CH₂)₉CH ₂CH₂—S), 3.03 (t, 2H, CH₃(CH₂)₉CH₂CH ₂—S), 7.35 (d, 1H),7.41 (s, 1H), 7.71 (s, 1H), 7.82 (d, 1H), 8.24 (d, 1H), (insg.5arom.CH), 11.67 (s, 1H, -Ph-OH—C(CH₃)₃—C(CH₃)₃)

¹³C-NMR (CDCl₃ 400 MHz): δ 14.1 (CH₃(CH₂)₁₁—S), 22.7 (CH₃ CH₂(CH₂)₁₀—S), 28.7˜29.7 (CH₃CH₂(CH₂)₈CH₂CH₂—S), 29.6(-Ph-OH—C(CH₃)₃—C(CH₃)₃), 31.5 (-Ph-OH—C(CH₃)₃—C(CH₃)₃), 31.9 (CH₃(CH₂)₉CH₂CH₂—S), 33.2 (-Ph-OH—C(CH₃)₃—C(CH₃)₃), 34.6 (CH₃(CH₂)₉CH₂ CH₂—S),35.7 (-Ph-OH—C(CH₃)₃—C(CH₃)₃), 113.6, 116.0, 117.6, 129.2, 143.4(CH_(arom)), 125.0, 141.2, 143.4 (C _(arom)), 137.9 (C _(arom)—S),125.2, 138.6 (C _(arom)—C(CH₃)₃), 146.6 (C _(arom)—OH)

<Synthesis Example 21> Synthesis of Compound 14

Compound 14 was synthesized by a synthesis method similar to that usedfor Compound 7, using Intermediate 4 (11.5 g, 52.1 mmol). The propertiesvalues are shown below.

FT-IR (KBr): 3057 cm⁻¹: O—H stretching vibration, 1437, 1391 cm⁻¹:triazole ring stretching vibration, 664 cm⁻¹: C—S stretching vibration

¹H-NMR (CDCl₃ 400 MHz): δ 0.81 (t, 3H, CH ₃(CH₂)₇—S), 1.20 (m, 8H,CH₃(CH ₂)₄(CH₂)₃—S), 1.30 (m, 2H, CH₃(CH₂)₄CH ₂(CH₂)₂—S), 1.49 (s, 9H,-Ph-OH—CH₃—C(CH ₃)₃), 1.54 (quin, 2H, CH₃(CH₂)₄CH₂CH ₂CH₂—S), 1.91(quin, 2H, S—CH₂CH ₂CH₂—S-Ph), 2.38 (s, 3H, -Ph-OH—CH ₃—C(CH₃)₃), 2.48(t, 2H, CH₃(CH₂)₄CH₂CH₂CH ₂—S), 2.68 (t, 2H, S—CH₂CH ₂CH₂—S-Ph), 3.17(t, 2H, S—CH₂CH₂CH ₂—S-Ph), 7.16 (s, 1H), 7.37 (d, 1H), 7.70 (s, 1H),7.81 (d, 1H), 8.05 (d, 1H), (insg.5arom. CH), 11.61 (s, 1H,-Ph-OH—CH₃—C(CH₃)₃)

¹³C-NMR (CDCl₃ 400 MHz): δ14.0 (CH₃(CH₂)₇—S), 20.1 (-Ph-OH—CH₃—C(CH₃)₃),22.6 (-Ph-OH—CH₃—C(CH₃)₃), 28.4 (CH₃ CH₂(CH₂)₆—S), 28.9 (CH₃(CH₂)₅CH₂CH₂—S), 29.2 (CH₃(CH₂)₃ CH₂ CH₂(CH₂)₂—S), 29.6 (CH₃(CH₂)₆ CH₂—S),30.9 (S—CH₂CH₂CH₂—S), 31.8 (CH₃CH₂ CH₂(CH₂)₅—S), 31.9(-Ph-OH—CH₃—C(CH₃)₃), 32.2 (S—CH₂ CH₂CH₂—S), 35.4 (S—CH₂CH₂ CH₂—S),114.4, 117.6, 119.3, 128.7, 129.4 (CH_(arom)), 141.3, 143.3 (C _(arom)),125.4 (C _(arom)—N), 128.3 (C_(arom)—CH₃), 137.1 (C _(arom)—S), 139.1 (C_(arom)—C(CH₃)₃), 146.7 (C _(arom)—OH)

<Synthesis Example 22> Synthesis of Compound 15

2-(2-Hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (36.3 g,0.115 mol), sec-butylmercaptan (20.8 g, 0.231 mol), potassium carbonate(35.0 g, 0.253 mol), and potassium iodide (1.3 g, 0.008 mol) wereallowed to react for 12 hours at 125° C. in 100 g of DMF. Aftercompletion of the reaction, the reaction liquid was subjected to pHadjustment, filtration, washing with MeOH, and washing with water, andrecrystallization was performed. Thus, Compound 15 was obtained.

FT-IR (KBr): 2961 cm⁻¹: O—H stretching vibration, 1448, 1391 cm⁻¹:triazole ring stretching vibration, 665 cm⁻¹: C—S stretching vibration

¹H-NMR (CDCl₃ 400 MHz): δ 1.06 (t, 3H, CH ₃CH₂CH(CH₃)—S), 1.37 (d, 3H,CH₃CH₂CH(CH ₃)—S), 1.49 (S, 9H, -Ph-OH—CH₃—C(CH ₃)₃), 1.61 (m, 2H, CH₃CH₂CH(CH₃)—S), 2.38 (s, 3H, -Ph-OH—CH ₃—C(CH₃)₃), 3.32 (m, 1H,CH₃CH₂CH(CH₃)—S), 7.17 (s, 1H), 7.42 (d, 1H), 7.80 (s, 1H), 7.84 (d,1H), 8.06 (d, 1H), (insg.5arom. CH), 11.62 (s, 1H, -Ph-OH—CH₃—C(CH₃)₃)

¹³C-NMR (CDCl₃ 400 MHz): δ 11.5 (CH₃CH₂CH(CH₃)—S), 20.3(CH₃CH₂CH(CH₃)—S), 20.9 (-Ph-OH—CH₃—C(CH₃)₃), 29.4 (CH₃ CH₂CH(CH₃)—S),29.5 (-Ph-OH—CH₃—C(CH₃)₃), 35.4 (-Ph-OH—CH₃—C(CH₃)₃), 44.6 (CH₃CH₂CH(CH₃)—S), 117.3, 117.5, 119.3, 128.3, 128.8 (CH_(arom)), 141.5, 143.2(C _(arom)), 125.4 (C _(arom)—N), 131.2 (C _(arom)—CH₃), 136.4 (C_(arom)—S), 139.1 (C _(arom)—C(CH₃)₃), 146.7 (C _(arom)—OH)

<Synthesis Example 23> Synthesis of Compound 16

2-(2-Hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (32.3 g,0.102 mol), cyclohexanethiol (23.8 g, 0.205 mol), potassium carbonate(31.1 g, 0.225 mol), and potassium iodide (1.2 g, 0.007 mol) wereallowed to react for 12 hours at 125° C. in 100 g of DMF. Aftercompletion of the reaction, the reaction liquid was subjected to pHadjustment, filtration, washing with MeOH, and washing with water, andrecrystallization was performed. Thus, Compound 16 was obtained.

FT-IR (KBr): 2930 cm⁻¹: O—H stretching vibration, 1450, 1391 cm⁻¹:triazole ring stretching vibration, 667 cm⁻¹: C—S stretching vibration

¹H-NMR (CDCl₃ 400 MHz): δ 1.40 (m, 4H, CH₂(CH ₂)₂(CH₂)₂CH—S), 1.49 (S,9H, -Ph-OH—CH₃—C(CH ₃)₃), 1.54 (m, 2H, CH ₂(CH₂)₂(CH₂)₂CH—S), 1.83 (m,2H, CH₂(CH₂)₂CH₂CH ₂CH—S), 2.06 (m, 2H, CH₂(CH₂)₂CH ₂CH₂CH—S), 2.38 (s,3H, -Ph-OH—CH ₃—C(CH₃)₃), 3.29 (m, 1H, CH₂CH₂CH₂CH—S), 7.17 (s, 1H),7.43 (d, 1H), 7.80 (s, 1H), 7.84 (d, 1H), 8.06 (d, 1H), (insg.5arom.CH), 11.62 (s, 1H, -Ph-OH—CH₃—C(CH₃)₃)

¹³C-NMR (CDCl₃ 400 MHz): δ 20.9 (-Ph-OH—CH₃—C(CH₃)₃), 25.7(CH₂(CH₂)₂(CH₂)₂CH—S), 26.0 (CH₂(CH₂)₂(CH₂)₂CH—S), 29.5(-Ph-OH—CH₃—C(CH₃)₃), 33.1 (CH₂(CH₂)₂(CH₂)₂CH—S), 35.4(-Ph-OH—CH₃—C(CH₃)₃), 46.3 (CH₂(CH₂)₂(CH₂)₂ CH—S), 117.2, 117.5, 119.3,128.3, 128.8 (CH_(arom)), 141.5, 143.2 (C _(arom)), 125.4 (C _(arom)—N),131.2 (C _(arom)—CH₃), 136.1 (C _(arom)—S), 139.1 (C _(arom)—C(CH₃)₃),146.7 (C _(arom)—OH)

<Synthesis Example 24> Synthesis of Compound 17

2-(2-Hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (50.0 g,0.158 mol), allylmercaptan (23.5 g, 0.317 mol), potassium carbonate(48.1 g, 0.348 mol), and potassium iodide (1.8 g, 0.011 mol) wereallowed to react for 12 hours at 125° C. in 125 g of DMF. Aftercompletion of the reaction, the reaction liquid was subjected to pHadjustment, filtration, washing with MeOH, and washing with water, andrecrystallization was performed. Thus, Compound 17 was obtained.

FT-IR (KBr): 3092 cm⁻¹: O—H stretching vibration, 2999 cm⁻¹: ═C—Hstretching vibration, 1449, 1390 cm⁻¹: triazole ring stretchingvibration, 664 cm⁻¹: C—S stretching vibration

¹H-NMR (CDCl₃ 400 MHz): δ 1.49 (S, 9H, -Ph-OH—CH₃—C(CH ₃)₃), 1.55 (m,2H, CH₂═CHCH ₂—S), 2.38 (s, 3H, -Ph-OH—CH ₃—C(CH₃)₃), 3.38 (m, 1H, CH₂═CHCH₂—S), 3.78 (m, 1H, CH ₂═CHCH₂—S), 4.23 (m, 1H, CH₂═CHCH₂—S), 7.16(s, 1H), 7.31 (d, 1H), 7.71 (s, 1H), 7.73 (d, 1H), 8.05 (d, 1H),(insg.5arom. CH), 11.66 (s, 1H, -Ph-OH—CH₃—C(CH₃)₃)

¹³C-NMR (CDCl₃ 400 MHz): δ 21.0 (-Ph-OH—CH₃—C(CH₃)₃), 22.5(CH₂═CHCH₂—S), 29.6 (-Ph-OH—CH₃—C(CH₃)₃), 35.4 (-Ph-OH—CH₃—C(CH₃)₃),41.8 (CH₂═CHCH₂—S), 46.3 (CH₂═CHCH₂—S), 116.7, 119.3, 123.3, 128.2,128.6 (CH_(arom)), 140.8, 141.7 (C _(arom)), 125.4 (C _(arom)—N), 124.1(C _(arom)—CH₃), 140.7 (C _(arom)—S), 139.0 (C _(arom)—C(CH₃)₃), 146.6(C _(arom)—OH)

<Synthesis Example 25> Synthesis of Compound 18

2-(2-Hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (25.0 g,79.2 mmol), p-toluenethiol (19.7 g, 158.3 mmol), potassium carbonate(24.1, 174.2 mmol), and potassium iodide (0.92 g, 5.54 mmol) wereallowed to react for 12 hours at 125° C. in 62.5 g of DMF. Aftercompletion of the reaction, the pH was adjusted, subsequently thereaction liquid was subjected to filtration, washing with MeOH, andwashing with water, and recrystallization was performed. Thus, Compound18 was obtained.

FT-IR (KBr): 3000 cm⁻¹: O—H stretching vibration, 1444, 1389 cm⁻¹:triazole ring stretching vibration, 667 cm⁻¹: C—S stretching vibration

¹H-NMR (CDCl₃ 400 MHz): δ1.48 (s, 9H, -Ph-OH—CH₃—C(CH ₃)₃), 2.37 (s, 3H,-Ph-OH—CH ₃—C(CH₃)₃), 2.40 (s, 3H, CH ₃-Ph-S—), 7.16 (s, 1H), 7.23 (s,2H), 7.32 (d, 1H), 7.43 (s, 2H), 7.56 (s, 1H), 7.81 (d, 1H), 8.02 (d,1H), (insg.9arom. CH), 11.56 (s, 1H, -Ph-OH—CH₃—C(CH₃)₃)

¹³C-NMR (CDCl₃ 400 MHz): δ20.9 (-Ph-OH—CH₃—C(CH₃)₃), 21.2 (CH₃-Ph-S—),29.5 (-Ph-OH—CH₃—C(CH₃)₃), 35.4 (-Ph-OH—CH₃—C(CH₃)₃), 115.3, 117.8,119.3, 128.7, 129.3 130.5, 133.7 (CH_(arom)), 125.4, 141.2, 143.4(C_(arom)), 128.3 (C _(arom)—CH₃), 138.9 (C _(arom)—S), 138.7 (S—^(C)_(arom)), 139.1 (C _(arom)—C(CH₃)₃), 146.7 (C _(arom)—OH)

<Synthesis Example 26> Synthesis of Compound 19

2-(2-Hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (20.0 g,63.3 mmol), benzylmercaptan (15.7 g, 126.6 mmol), potassium carbonate(19.3 g, 139.4 mmol), and potassium iodide (0.74 g, 4.5 mmol) wereallowed to react for 9 hours at 125° C. in 50.0 g of DMF. Aftercompletion of the reaction, the pH was adjusted, subsequently thereaction liquid was subjected to filtration, washing with MeOH, andwashing with water, and recrystallization was performed. Thus, Compound19 was obtained.

FT-IR (KBr): 2960 cm⁻¹: O—H stretching vibration, 1441, 1392 cm⁻¹:triazole ring stretching vibration, 664 cm⁻¹: C—S stretching vibration

¹H-NMR (CDCl₃ 400 MHz): δ1.49 (s, 9H, -Ph-OH—CH₃—C(CH ₃)₃), 2.38 (s, 3H,-Ph-OH—CH ₃—C(CH₃)₃), 4.24 (s, 2H, Ph-CH ₂—S—), 7.16 (s, 1H), 7.26˜7.38(m, 6H), 7.72 (s, 1H), 7.80 (d, 1H), 8.04 (d, 1H), (insg.10_(arom). CH),11.58 (s, 1H, -Ph-OH—CH₃—C(CH₃)₃)

¹³C-NMR (CDCl₃ 400 MHz): δ20.9 (-Ph-OH—CH₃—C(CH₃)₃), 29.5(-Ph-OH—CH₃—C(CH₃)₃), 35.4 (-Ph-OH—CH₃—C(CH₃)₃), 38.6 (Ph-CH₂—S—),115.4, 117.6, 119.3, 128.7, 128.8, 128.8, 129.7, 137.0 (CH_(arom)),125.4, 141.4, 143.4 (C _(arom)), 128.3 (C _(arom)—CH₃), 136.5 (C _(arom)CH₂—S—), 138.7 (S—C _(arom)), 139.1 (C _(arom)—C(CH₃)₃), 146.7 (C_(arom)—OH)

<Synthesis Example 27> Synthesis of Compound 20

2-(2-Hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (50.5 g,0.160 mol), 2-mercaptoethanol (25.0 g, 0.320 mol), potassium carbonate(48.6 g, 0.352 mol), and potassium iodide (1.9 g, 0.011 mol) wereallowed to react for 12 hours at 125° C. in 125 g of DMF. Aftercompletion of the reaction, the reaction liquid was subjected to pHadjustment, filtration, washing with MeOH, and washing with water, andrecrystallization was performed. Thus, compound 20 was obtained.

FT-IR (KBr): 3350 cm⁻¹: O—H stretching vibration, 1437, 1392 cm⁻¹:triazole ring stretching vibration, 666 cm⁻¹: C—S stretching vibration

¹H-NMR (CDCl₃ 400 MHz): δ 1.49 (S, 9H, -Ph-OH—CH₃—C(CH ₃)₃), 2.38 (s,3H, -Ph-OH—CH ₃—C(CH₃)₃), 2.79 (t, 2H, HOCH₂CH ₂—S), 3.25 (t, 2H, HOCH₂CH₂—S), 7.17 (s, 1H), 7.41 (d, 1H), 7.83 (s, 1H), 7.84 (d, 1H), 8.05(d, 1H), (insg.5arom. CH), 11.56 (s, 1H, -Ph-OH—CH₃—C(CH₃)₃)

¹³C-NMR (CDCl₃ 400 MHz): δ 20.9 (-Ph-OH—CH₃—C(CH₃)₃), 29.5(-Ph-OH—CH₃—C(CH₃)₃), 35.4 (-Ph-OH—CH₃—C(CH₃)₃), 36.8 (HOCH₂ CH₂—S),60.3 (HOCH₂CH₂—S), 115.8, 118.0, 119.3, 128.4, 129.7 (CH_(arom)), 141.5,143.2 (C _(arom)), 125.3 (C _(arom)—N), 128.9 (C _(arom)—CH₃), 135.7 (C_(arom)—S), 139.2 (C _(arom)—C(CH₃)₃), 146.7 (C _(arom)—OH)

<Synthesis Example 28> Synthesis of Compound 21

2-(2-Hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (10.0 g,31.7 mmol), hexanedithiol (4.76 g, 31.7 mmol), potassium carbonate (8.75g, 63.3 mmol), and potassium iodide (0.37 g, 2.2 mmol) were allowed toreact for 12 hours at 130° C. in 50 mL of DMF. After completion of thereaction, toluene was added thereto, and the reaction liquid wassubjected to washing with water, distillation of the solvent, andrecrystallization. Thus, Compound 21 was obtained.

FT-IR (KBr): 3009 cm⁻¹: O—H stretching vibration, 1431, 1391 cm⁻¹:triazole ring stretching vibration, 656 cm⁻¹: C—S stretching vibration

¹H-NMR (CDCl₃ 400 MHz): δ1.49 (s, 18H, (-Ph-OH—CH₃—C(CH ₃)₃)₂), 1.55 (m,4H, —S—CH₂CH ₂CH₂CH₂CH₂CH₂—S—), 1.77 (m, 4H, —S—CH₂CH ₂CH₂CH₂CH₂CH₂—S—), 2.38 (s, 6H, (-Ph-OH—CH ₃—C(CH₃)₃)₂), 3.04 (t, 4H, —S—CH₂CH₂CH₂CH₂CH₂CH ₂—S—), 7.16 (s, 2H), 7.37 (d, 2H), 7.70 (s, 2H), 7.81(d, 2H), 8.05 (s, 2H) (insg.10arom. CH), 11.60 (s, 2H,-Ph-OH—CH₃—C(CH₃)₃)

¹³C-NMR (CDCl₃ 400 MHz): δ20.9 (-Ph-OH—CH₃—C(CH₃)₃)₂, 28.4(-Ph-OH—CH₃—C(CH₃)₃)₂, 28.6 (—S—CH₂CH₂ CH₂ CH₂CH₂CH₂—S—), 29.5(-Ph-OH—CH₃—C(CH₃)₃)₂, 33.1 (—S—CH₂ CH₂CH₂CH₂ CH₂CH₂—S—), 35.4(—S—CH₂CH₂CH₂CH₂CH₂ CH₂—S—), 113.7, 117.6, 119.3, 128.3, 129.3(CH_(arom)), 141.2, 143.4 (C _(arom)), 125.4 (C _(arom)—N), 128.3 (C_(arom)—CH₃), 137.7 (C _(arom)—S), 139.1 (C _(arom)—C(CH₃)₃), 146.7 (C_(arom)—OH)

<Synthesis Example 29> Synthesis of Compound 22

2,4-Dihydroxybenzophenone (8.6 g, 40 mmol),1,4-diazabicyclo[2.2.2]octane (9.0 g, 80 mmol), anddimethylthiocarbamoyl chloride (6.18 g, 50 mmol) were allowed to reactfor 12 hours at 80° C. in 100 mL of DMF. After completion of thereaction, toluene was added to the reaction mixture, and the mixture wassubjected to washing with water, distillation of the solvent, andpurification using a column. Thus, Intermediate 11 as described belowwas obtained.

Intermediate 11 (5.0 g, 16.6 mmol) was allowed to react for 40 minutesat 240° C. in 10 mL of sulfolane. After completion of the reaction,toluene was added thereto, and the mixture was subjected to washing withwater, distillation of the solvent, and purification using a column.Thus, Intermediate 12 as described below was obtained.

Intermediate 12 (3.46 g, 11.4 mmol) and potassium hydroxide (3.22 g,57.4 mmol) were allowed to react for 6 hours in 100 mL of ethanol, whilethe mixture was heated to reflux. After completion of the reaction, thereaction mixture was acidified with hydrochloric acid, toluene was addedthereto, and the mixture was subjected to washing with water,distillation of the solvent, and purification using a column. Thus,Compound 22 was obtained.

FT-IR (KBr): 3055 cm⁻¹: O—H stretching vibration, 2559 cm⁻¹: S—Hstretching vibration, 1624 cm⁻¹: C═O stretching vibration

¹H-NMR (CDCl₃ 400 MHz): δ 3.65 (s, 1H, -Ph-OH—SH), 6.68 (d, 1H), 6.93(s, 1H), 7.44 (d, 1H), 7.51 (m, 2H), 7.58 (m, 1H), 7.65 (d, 2H)(insg.8arom. CH), 12.28 (s, 1H, -Ph-OH—SH)

¹³C-NMR (CDCl₃ 400 MHz): δ 115.4, 117.5, 127.4, 128.0 (CH_(arom)), δ130.9, 132.9 (C _(arom)), δ 142.26 (C _(arom)SH), δ 162.5 (C_(arom)—OH), δ 199.6 (C(═O))

<Synthesis Example 30> Synthesis of Compound 23

4-Chloro-4′-hydroxybenzophenone (5.44 g, 23.4 mmol), octanethiol (6.84g, 46.8 mmol), and potassium carbonate (13.7 g, 99.2 mmol) were allowedto react for 4 hours at 200° C. in 2 mL of N-methylpyrrolidone. Aftercompletion of the reaction, toluene was added thereto, and the mixturewas subjected to washing with water, distillation of the solvent, andpurification using a column. Thus, Compound 23 was obtained.

FT-IR (KBr): 3266 cm⁻¹: O—H stretching vibration, 1630 cm⁻¹: C═Ostretching vibration, 646 cm⁻¹: C—S stretching vibration

¹H-NMR (CDCl₃ 400 MHz): δ 0.88 (t, 3H, CH ₃(CH₂)₇—S), 1.28 (m, 8H,CH₃(CH ₂)₄(CH₂)₃—S), 1.45 (m, 2H, CH₃(CH₂)₄CH ₂CH₂CH₂—S), 1.71 (quin,2H, CH₃(CH₂)₅CH ₂CH₂—S), 3.00 (t, 2H, CH₃(CH₂)₅CH₂CH ₂—S), 6.22 (s, 1H,—S-Ph-C═O-Ph-OH), 6.92 (d, 2H), 7.31 (d, 2H), 7.68 (d, 2H), 7.74 (d, 2H)(insg.8arom. CH)

¹³C-NMR (CDCl₃ 400 MHz): δ14.1 (CH₃(CH₂)₇—S), 22.6 (CH₃ CH₂(CH₂)₅—S),28.8 (CH₃(CH₂)₄ CH₂(CH₂)₂—S), 28.9 (CH₃(CH₂)₃ CH₂(CH₂)₃—S), 29.1 (CH₃CH₂CH₂(CH₂)₄—S), 31.8 (CH₃ CH₂CH₂(CH₂)₄—S), 32.2 (CH₃(CH₂)₆ CH₂—S), 115.3,126.3, 130.5, 132.8 (CH_(arom)), 134.4 (C _(arom)), 143.9 (C _(arom)S—),160.3 (C _(arom)—OH), 195.4 (Ph-C(═O)-Ph)

<Synthesis Example 31> Synthesis of Compound 24

Intermediate 3 (1.20 g, 4.7 mmol), Compound 22 (2.00 g, 8.6 mmol), andpotassium carbonate (2.40 g, 17.2 mmol) were allowed to react for 6hours in 30 mL of acetonitrile, while the mixture was heated to reflux.After completion of the reaction, toluene was added thereto, and themixture was washed with water, distillation of the solvent, andpurification using a column. Thus, Compound 24 was obtained.

FT-IR (KBr): 3059 cm⁻¹: O—H stretching vibration, 1615 cm⁻¹: C═Ostretching vibration, 669 cm⁻¹: C—S stretching vibration

¹H-NMR (CDCl₃ 400 MHz): δ 0.88 (t, 3H, CH ₃(CH₂)₇—S), 1.28 (m, 4H,CH₃(CH ₂)₄(CH₂)₃—S), 1.37 (m, 2H, CH₃(CH₂)₄CH ₂(CH₂)₂—S), 1.58 (m, 2H,CH₃(CH₂)₅CH ₂CH₂—S), 2.00 (quin, 2H, S—CH₂CH ₂CH₂—S-Ph), 2.51 (t, 2H,CH₃(CH₂)₅CH₂CH ₂—S), 2.67 (t, 2H, S—CH ₂CH₂CH₂—S-Ph), 3.12 (t, 2H,S—CH₂CH₂CH ₂—S-Ph), 6.71 (d, 1H), 6.90 (s, 1H), 7.44 (d, 1H), 7.51 (m,2H), 7.58 (m, 1H), 7.65 (d, 2H) (insg.8arom. CH), 12.37 (s, 1H,-Ph-OH—S—)

¹³C-NMR (CDCl₃ 400 MHz): δ14.1 (CH₃(CH₂)₇—S), 22.7 (CH₃ CH₂(CH₂)₆—S),28.3 (CH₃(CH₂)₃ CH₂(CH₂)₃—S), 28.9 (CH₃(CH₂)₅ CH₂CH₂—S), 29.2 (CH₃(CH₂)₃CH₂ CH₂(CH₂)₂—S), 29.7 (CH₃(CH₂)₆ CH₂—S), 30.1 (S—CH₂CH₂CH₂—S), 30.9(S—CH₂ CH₂CH₂—S), 31.8 (CH₃CH₂ CH₂(CH₂)₅—S), 32.2 (S—CH₂CH₂ CH₂—S),114.1, 116.0, 116.7, 128.4, 129.0, 131.8, 133.5 (CH_(arom)), 130.9,132.9 (C _(arom)), 138.0 (C _(arom)S—), 163.7 (C _(arom)—OH), 200.5(Ph-C(═O)-Ph)

<Synthesis Example 32> Synthesis of Compound 25

4-Chloro-4′-hydroxybenzophenone (1.68 g, 7.2 mmol), Intermediate 4 (2.54g, 11.5 mmol), and potassium carbonate (1.60 g, 11.5 mmol) were allowedto react for 4 hours at 200° C. in 2 mL of N-methylpyrrolidone. Aftercompletion of the reaction, toluene was added thereto, and the mixturewas subjected to washing with water, distillation of the solvent, andpurification using a column. Thus, Compound 25 was obtained as a liquidcontaining 90% or more of the compound.

FT-IR (KBr): 3266 cm⁻¹: O—H stretching vibration, 1630 cm⁻¹: C═Ostretching vibration, 646 cm⁻¹: C—S stretching vibration

¹H-NMR (CDCl₃ 400 MHz): δ 0.80 (t, 3H, CH ₃(CH₂)₇—S), 1.20 (m, 8H,CH₃(CH ₂)₄(CH₂)₃—S), 1.30 (m, 2H, CH₃(CH₂)₄CH ₂CH₂CH₂—S), 1.50 (quin,2H, CH₃(CH₂)₅CH ₂CH₂—S), 1.91 (quin, 2H, S—CH₂CH ₂CH₂—S-Ph), 2.43 (t,2H, CH₃(CH₂)₆CH ₂—S), 2.60 (t, 2H, S—CH ₂CH₂CH₂—S-Ph), 3.00 (t, 2H,S—CH₂CH₂CH ₂—S-Ph), 5.93 (s, 1H, -Ph-C═O-Ph-OH), 6.83 (d, 2H), 7.30 (d,2H), 7.68 (d, 2H), 7.63 (d, 2H) (insg.8arom. CH)

¹³C-NMR (CDCl₃ 400 MHz): δ14.1 (CH₃(CH₂)₇—S), 22.6 (CH₃ CH₂(CH₂)₆—S),28.5 (CH₃(CH₂)₂ CH₂(CH₂)₃—S), 28.9 (CH₃(CH₂)₅ CH₂CH₂—S), 29.2 (CH₃(CH₂)₃CH₂ CH₂(CH₂)₂—S), 29.7 (CH₃(CH₂)₆ CH₂—S), 30.9 (S—CH₂CH₂CH₂—S), 31.0(S—CH₂ CH₂CH₂—S), 31.8 (CH₃CH₂ CH₂(CH₂)₅—S), 32.4 (S—CH₂CH₂ CH₂—S),114.4, 125.5, 128.6, 129.6 (CH_(arom)), 131.9, 133.2 (C _(arom)), 142.3(C _(arom)S—), 159.8 (C _(arom)—OH), 194.5 (Ph-C(═O)-Ph)

<Synthesis Example 33> Synthesis of Compound 26

Salicylic acid (8.8 g, 63.9 mmol) and thionyl chloride (22.8 g, 191.6mmol) were allowed to react for 3 hours at 25° C., and then unreactedthionyl chloride was distilled off under reduced pressure. Thus,salicylic acid chloride (9.8 g, 62.6 mmol) as an intermediate wasobtained. Salicylic acid chloride (2.50 g, 16.0 mmol) thus obtained,Intermediate 6 (3.86 g, 18.35 mmol), and potassium carbonate (2.20 g,15.91 mmol) were allowed to react for 12 hours in 100 mL of toluene,while the mixture was heated to reflux. After completion of thereaction, toluene was added thereto, and the mixture was subjected towashing with water, distillation of the solvent, and purification usinga column. Thus, Compound 26 was obtained as a liquid.

FT-IR (KBr): 3229 cm⁻¹: O—H stretching vibration, 1694 cm⁻¹: C═O—Ostretching vibration, 593 cm⁻¹: C—S stretching vibration

¹H-NMR (CDCl₃ 400 MHz): δ 0.88 (t, 3H, CH ₃(CH₂)₅—S), 1.29 (m, 4H,CH₃(CH ₂)₂(CH₂)₃—S), 1.45 (m, 2H, CH₃(CH₂)₂CH ₂(CH₂)₂—S), 1.67 (quin,2H, CH₃(CH₂)₃CH ₂CH₂—S), 2.96 (t, 2H, CH₃(CH₂)₃CH₂CH ₂—S), 6.99 (m, 2H),7.05 (d, 1H), 7.14 (s, 1H), 7.22 (d, 1H), 7.25 (t, 1H), 7.56 (t, 1H),8.01 (d, 1H), (insg.8arom. CH), 10.47 (s, 1H, -Ph-OH)

¹³C-NMR (CDCl₃ 400 MHz): δ 14.0 (CH₃(CH₂)₅—S), 22.5 (CH₃ CH₂(CH₂)₄—S),28.9 (CH₃CH₂(CH₂)₂CH₂CH₂—S), 31.3 (CH₃(CH₂)₃ CH₂CH₂—S), 33.3 (CH₃(CH₂)₄CH₂—S), 111.8, 118.6, 119.5, 121.2, 129.2, 130.3 (CH_(arom)), 117.9 (C_(arom)—C(═O)—O—), 139.5 (C _(arom)—S), 150.4 (—(O═)C—O—C _(arom)), δ162.3 (C _(arom)—OH), δ 168.7 (C(═O)—)

<Synthesis Example 34> Synthesis of Compound 27

Compound 27 was synthesized by a synthesis method similar to that usedfor Compound 26, using 3,5-di-tert-butyl-4-hydroxybenzoic acid (16.0 g,63.9 mmol).

FT-IR (KBr): 3622 cm⁻¹: O—H stretching vibration, 1732 cm⁻¹: C═O—Ostretching vibration, 639 cm⁻¹: C—S stretching vibration

¹H-NMR (CDCl₃ 400 MHz): δ 0.88 (t, 3H, CH ₃(CH₂)₅—S), 1.29 (m, 4H,CH₃(CH ₂)₂(CH₂)₃—S), 1.43 (m, 2H, CH₃(CH₂)₂CH ₂(CH₂)₂—S), 1.49 (s, 18H,-Ph-OH—(C(CH ₃)₃)₂), 1.67 (quin, 2H, CH₃(CH₂)₃CH ₂CH₂—S), 2.93 (t, 2H,CH₃(CH₂)₃CH₂CH ₂—S), 5.77 (s, 1H, -Ph-OH—(C(CH₃)₃)₂), 6.98 (d, 1H), 7.13(s, 1H), 7.17 (d, 1H), 7.30 (t, 1H), 8.04 (s, 2H) (insg.6arom. CH)

¹³C-NMR (CDCl₃ 400 MHz): δ 14.0 (CH₃(CH₂)₆—S), 22.5(-Ph-OH—(C(CH₃)₃)₂)), 28.5 (CH₃ CH₂(CH₂)₄—S), 28.9 (CH₃(CH₂)₂CH₂(CH₂)₂—S), 30.2 (-Ph-OH—(C(CH₃)₃)₂)), 31.3 (CH₃CH₂ CH₂(CH₂)₂CH₂—S),33.4 (CH₃(CH₂)₃ CH₂CH₂—S), 34.1 (CH₃(CH₂)₄ CH₂—S), 119.1, 120.3, 121.8,127.8, 129.4 (CH_(arom)), 125.7 (C _(arom)—C(═O)—O—), 136.0 (—C_(arom)—(C(CH₃)₃)₂), 138.8 (C _(arom)—S), 151.5 (—(O═)C—O—C _(arom)), δ158.8 (C _(arom)—OH), δ 165.5 (C(═O)—)

<Synthesis Example 35> Synthesis of Compound 28

2-Chloro-4,6-diphenyl-1,3,5-triazine (1.92 g, 7.14 mmol) and aluminumchloride (2.37 g, 17.85 mmol) were reacted for 30 minutes at 25° C. in50 mL of O-xylene, and then Intermediate 5 (2.00 g, 14.25 mmol) wasadded thereto. The mixture was allowed to react for 8 hours at 80° C.After completion of the reaction, toluene was added thereto, and themixture was subjected to washing with water, distillation of thesolvent, purification using a column, and recrystallization. Thus,Compound 28 was obtained.

FT-IR (KBr): 3064 cm⁻¹: O—H stretching vibration, 1568, 845 cm⁻¹:triazine ring stretching vibration, 602 cm⁻¹: C—S stretching vibration

¹H-NMR (CDCl₃ 400 MHz): δ 2.41 (s, 3H, Ph-SCH ₃), 6.71 (m, 2H), 7.47 (m,6H), 8.47 (m, 5H) (insg.13arom. CH), 13.28 (s, 1H, Ph-OH)

¹³C-NMR (CDCl₃ 400 MHz): δ 14.7 (Ph-SCH ₃), 114.1((HO—)C_(arom)C_(arom)C(—N)═N), 113.2, 128.8, 129.0, 129.8, 133.0(CH_(arom)), 148.2 (C _(arom)—SCH₃), 162.4 (C _(arom)—OH), 171.4(N—(C_(arom))—C═N).

<Synthesis Example 36> Synthesis of Compound 29

Cyanuric acid chloride (1.92 g, 7.14 mmol) and Intermediate 6 (6.75 g,32.13 mmol) were heated to dissolve in 50 mL of 1,2-dichloroethane, andthen the solution was cooled in ice. Aluminum chloride (0.95 g, 7.14mmol) was added thereto over 30 minutes, and the mixture was allowed toreact for 54 hours at 70° C. After completion of the reaction, toluenewas added thereto, and the mixture was subjected to washing with water,distillation of the solvent, purification using a column, andrecrystallization. Thus, Compound 29 was synthesized.

FT-IR (KBr): 3064 cm⁻¹: O—H stretching vibration, 1568, 846 cm⁻¹:triazine ring stretching vibration, 602 cm⁻¹: C—S stretching vibration

¹H-NMR (CDCl₃ 400 MHz): δ 0.92 (t, 3H, CH ₃(CH₂)₅—S), 1.34 (m, 4H, CH₃(CH ₂)₂(CH₂)₃—S), 1.47 (quin, 2H, CH₃(CH₂)₂CH ₂(CH₂)₂—S), 1.75 (quin,2H, CH₃(CH₂)₃CH ₂CH₂—S), 3.02 (t, 2H, CH₃(CH₂)₃CH₂CH ₂—S), 6.89 (d, 2H),7.62 (m, 6H), 8.58 (d, 1H), 8.63 (m, 4H) (insg.13arom. CH), 13.43 (s,1H, Ph-OH)

¹³C-NMR (CDCl₃ 400 MHz): δ 14.0 (CH₃(CH₂)₅—S), 22.5 (CH₃ CH₂(CH₂)₄—S),28.6 (CH₃CH₂ CH₂(CH₂)₃—S), 28.7 (CH₃(CH₂)₂CH₂(CH₂)₂—S), 31.4 (CH₃(CH₂)₃CH₂CH₂—S), 31.5 (CH₃(CH₂)₄ CH₂—S), 111.9 (C _(arom)C═N), 114.1, 117.9,128.5 (CH_(arom)), 149.6 (C _(arom)—S), 162.7 (C _(arom)—OH), 168.4 (C_(arom)—C═N).

<Synthesis Example 37> Synthesis of Compound 30

Compound 30 was synthesized by a synthesis method similar to that usedfor Compound 29, using Intermediate 7 (7.66 g, 32.13 mmol). FT-IR (KBr):2951 cm⁻¹: O—H stretching vibration, 1570, 843 cm⁻¹: triazine ringstretching vibration, 606 cm⁻¹: C—S stretching vibration

¹H-NMR (CDCl₃ 400 MHz): δ 0.90 (t, 3H, CH ₃(CH₂)₇—S), 1.32 (m, 8H,CH₃(CH ₂)₄(CH₂)₃—S), 1.47 (quin, 2H, CH₃(CH₂)₄CH ₂(CH₂)₂—S), 1.72 (quin,2H, CH₃(CH₂)₅CH ₂CH₂—S), 2.92 (t, 2H, CH₃(CH₂)₆CH ₂—S), 6.70 (d, 2H),7.72 (d, 1H), (insg.13arom. CH), 12.99 (s, 1H, Ph-OH)

¹³C-NMR (CDCl₃ 400 MHz): δ 14.1 (CH₃(CH₂)₇—S), 22.7 (CH₃ CH₂(CH₂)₆—S),28.6 (CH₃CH₂ CH₂(CH₂)₅—S), 29.2 (CH₃(CH₂)₂(CH₂)₃(CH₂)₂—S), 31.5(CH₃(CH₂)₅ CH₂CH₂—S), 31.9 (CH₃(CH₂)₆ CH₂—S), 111.8 (C _(arom)C═N),113.9, 117.7, 128.4 (CH_(arom)), 149.6 (C _(arom)—S), 162.7 (C_(arom)—OH), 168.2 (C_(arom)—C═N)

<Synthesis Example 38> Synthesis of Compound 31

Compound 31 was synthesized by a synthesis method similar to that usedfor Compound 28, using Intermediate 6 (2.0 g, 8.38 mmol). The propertiesvalues are shown below.

FT-IR (KBr): 33064 cm⁻¹: O—H stretching vibration, 1568, 846 cm⁻¹:triazine ring stretching vibration, 602 cm⁻¹: C—S stretching vibration

¹H-NMR (CDCl₃ 400 MHz): δ 0.90 (t, 3H, CH ₃(CH₂)₅—S), 1.34 (m, 2H, CH₃(CH ₂)₂(CH₂)₃—S), 1.47 (quin, 2H, CH₃(CH₂)₂CH ₂(CH₂)₂—S), 1.75 (quin,2H, CH₃(CH₂)₃CH ₂CH₂—S), 3.03 (t, 2H, CH₃(CH₂)₃CH₂CH ₂—S), 6.89 (d, 2H),7.62 (m, 6H), 8.58 (d, 1H), 8.63 (m, 4H) (insg.13arom. CH), 13.43 (s,1H, Ph-OH)

¹³C-NMR (CDCl₃ 400 MHz): δ 14.0 (CH₃(CH₂)₅—S), 22.5 (CH₃ CH₂(CH₂)₄—S),28.7 (CH₃CH₂ CH₂(CH₂)₃—S), 28.8 (CH₃(CH₂)₂ CH₂(CH₂)₂—S), 31.4 (CH₃(CH₂)₃CH₂CH₂—S), 31.8 (CH₃(CH₂)₄ CH₂—S), 114.3 ((HO—)CC _(arom)C(—N)═N),117.9, 129.0, 129.9, 133.0 (CH_(arom)), 135.3 (C _(arom)—C═N), 147.4 (C_(arom)—S), 162.3 (C _(arom)—OH), 171.4 (C _(arom)—C═N).

Meanwhile, Compound 5 was a compound manufactured by Sigma-AldrichCompany; Compound 32 was a compound manufactured by BASF SE; Compound 33was a compound manufactured by Tokyo Chemical Industry Co., Ltd.;Compound 34 was a compound manufactured by Wako Pure ChemicalIndustries, Ltd.; Compound 35 was a compound manufactured bySigma-Aldrich Company; and Compound 36 was a compound manufactured byTokyo Chemical Industry Co., Ltd.

Evaluation results for the melting points, film external appearance, andrefractive indices of the compounds of Examples and Comparative Examplesare presented in Table 1 to Table 8, and the ultraviolet-visibletransmission spectra of the compounds of Examples are presented in FIG.1 to FIG. 8.

1. Evaluation of Compounds

(1) Melting Point

Melting points of the compounds of Examples and Comparative Examples 2to 4 were measured by visual observation (liquid or solid) at roomtemperature (25° C.), or using a micro-melting point apparatus (MP-3manufactured by Yanako Co., Ltd.) or a differential scanning calorimeter(DSC6220 manufactured by Seiko Instruments Inc.) (Tables 1 to 7).

In benzotriazole compounds each having a thiol group, when the number ofcarbon atoms of the functional group —(CH₂)_(n)—SH was from 1 to 10, themelting point became 35° C. or lower (Compounds 1 and 2). For compoundscontaining a thioether group in a phenyl group (R^(1a) to R^(5a)) inbenzotriazole (Compounds 3 and 4) in regard to benzotriazole compounds,and for compounds containing a thioether group in benzophenone(Compounds 24 and 25) and salicylate-based compounds (Compounds 26 and27), the maximum number of carbon atoms in the functional group—(CH₂)_(n)—S—, —S—(CH₂)_(n)—S—, or —S—(CH₂)_(n)CH₃ was 8 or less. Thus,it was confirmed that the melting point was 35° C. or lower, thecompounds were liquid at normal temperature, and there was a correlationbetween the number of carbon atoms and the melting point, regardless ofhaving a benzotriazole skeleton, a benzophenone skeleton, or asalicylate skeleton. On the other hand, in regard to benzotriazole-basedcompounds each having a thioether group composed of a linear saturatedaliphatic hydrocarbon group in the benzotriazole group (R^(6a) toR^(9a)) (Compounds 6 to 14), compounds in which the maximum number ofcarbon atoms in the functional group —(CH₂)_(n)—S—, —S—(CH₂)_(n)—S—, or—S—(CH₂)_(n)CH₃ is 18 or less (Compounds 6 to 14) have melting points of91° C. or lower; however, there is no clear correlation between thenumber of carbon atoms and the melting point, and it is difficult tolower the melting point.

Furthermore, when compared to Compound 32 having an ether group (—O—),Compound 3 having a thioether group (—S—) had a low melting point andwas liquid at normal temperature. Furthermore, compared to Compounds 6to 13 each having one thioether group, Compound 14 having two thioethergroups had a lower melting point, so that a tendency of lowering themelting point by introduction of thioether was confirmed.

On the other hand, triazine-based Compound 28 had an increased meltingpoint by having a sulfur-containing group introduced thereinto, and thusit was suggested that the compound had excellent heat resistance.

(2) Refractive Index

For Compounds 1, 2, 3, 4, 5, 25, 26, and 27 having melting points of 25°C. or lower, the refractive indices were measured at 20° C.; and forCompound 14 having a relatively low melting point (46° C.) and Compound24 (34° C.), the refractive indices were measured after the compoundswere heated, using an Abbe refractometer (NAR-2T manufactured by AtagoCo., Ltd.) in all cases. Also, for Comparative Examples 2, 3 and 4(Compounds 32, 33 and 34), the catalogue values provided by themanufacturers are described in the tables.

In regard to benzotriazole-based compounds, Compounds 1 to 4 and 14 hadhigher refractive indices compared to Compounds 5 and 32; in regard tobenzophenone-based compounds, Compounds 24 and 25 had higher refractiveindices compared to Compound 33; and in regard to salicylate-basedcompounds, Compounds 26 and 27 had higher refractive indices compared toCompound 34. Thus, an effect of imparting a high refractive index byintroducing a sulfur-containing group was confirmed.

(3) 5% Weight Reduction Temperature

For Compounds 6 to 21, 23, 24, 27, 29, 30, 31, 33, 34, 35 and 36,measurement was performed in a measurement range of 25° C. to 550° C. ata temperature increasing temperature of 10° C./min, using athermogravimetric/differential thermal analyzer (manufactured by SeikoInstruments Inc., TG/DTA 6200), and thus the temperature at which weightchange (TG) occurred as reduction by 5 weight % was read.

In benzotriazole-based compounds having thioether groups composed ofsaturated and unsaturated hydrocarbon groups (Compounds 6 to 17),aromatic groups (Compounds 18 and 19), and oxygen-containing hydrocarbongroups (Compound 20) and a bis-form (Compound 21), heat resistance wasincreased by introducing thioether groups (suppressing deterioration ofthe ultraviolet absorbency and the ability of increasing refractiveindex of resin members, and deterioration of transparency of transparentresins, caused by thermal decomposition of ultraviolet absorbers). Also,their 5% weight reduction degradation temperatures were higher than thevalues of 2-(2-hydroxy-3-t-butyl-5-methylphenyl)chlorobenzotriazole(Compound 36, 5% weight reduction temperature: 230° C.) and Compound 5(5% weight reduction temperature: 249° C.), which do not havesulfur-containing groups and are generally used as ultraviolet absorbersfor long wavelength absorption, and their 5% weight reductiontemperatures were 252° C. or higher. Similarly, also in regard tobenzophenone and salicylate-based compounds, benzophenone-basedcompounds 23 (5% weight reduction temperature: 279° C.) and 24 (5%weight reduction temperature: 260° C.) had 5% weight reductiontemperatures of 260° C. or higher and had enhanced heat resistance,compared to Compound 33 having no thioether group (5% by weightreduction temperature: 249° C.); and salicylate-based compound 27 (5%weight reduction temperature: 264° C.) had a 5% weight reductiondegradation temperature of 260° C. or higher and had enhanced heatresistance, compared to Compound 34 having no thioether group (5% weightreduction temperature: 249° C.). That is, the 5% weight reductiontemperatures of Compounds 6 to 21, 23, 24, and 27 were higher than 100°C. to 250° C., in which range the softening points of most generalresins fall (“Well-Known Plastics”, reviewed by Japan Plastics IndustryFederation, published by Nippon Jitsugyo Publishing Co., Ltd.), andgenerally, the molding processing temperature of 100° C. to 200° C. canbe applied to thermosetting resins and thermoplastic resins whichrequire molding processing temperatures higher than 200° C. to 250° C.,as well as thermosetting resins of which molding processing temperaturesare general range of 100° C. to 200° C. Thus, deterioration of theultraviolet absorbency and the ability of increasing refractive index ofa resin member and transparency of a transparent resin member can besuppressed.

Also, in regard to triazine-based compounds, as compared to Compound 35having no thioether group (5% weight reduction temperature: 319° C.),Compound 29 (5% weight reduction temperature: 369° C.), Compound 30 (5%weight reduction temperature: 372° C.), and Compound 31 (5% weightreduction temperature: 336° C.), all having thioether groups introducedthereinto, had increased 5% weight reduction temperatures as a result ofintroducing thioether groups, and had enhanced heat resistance(deterioration of the ultraviolet absorbency and the ability ofincreasing refractive index of a resin member and deterioration oftransparency of a transparent resin, all caused by thermal decompositionof an ultraviolet absorber, were suppressed). Thus, it was confirmedthat their compounds having thioether group is applicable tothermoplastic resins which require molding processing temperatureshigher than 200° C. to 250° C.

(4) Ultraviolet Absorption

Each of Compounds 1 to 5, 8, 10, 11, 14, and 22 to 35 was diluted withchloroform to 5 μM, and the dilution was accommodated in a 10-mm quartzcell. The absorption spectrum was measured using an ultraviolet-visiblespectrophotometer (V-550 manufactured by JASCO Corp.) (FIGS. 1, 2 and 6to 8). Furthermore, Compounds 6 to 21 and 36 were measured in the samemanner using chloroform at 100 μM (FIGS. 3 to 5).

From each of the absorption spectra (100 μM) of Compounds 8, 10, 11, 14,21, and 36, an intersection point between the absorption spectrum on thelong wavelength side for an absorption peak at 350 to 390 nm and thebaseline (a line having a slope of 0 in the absorption spectrum at 430to 500 nm) was designated as a peak end (e.g.: FIG. 3, Example 47), andthereby an absolute value of the slope on the long wavelength side ofthe absorption peak in the wavelength region of 350 to 390 nm wasdetermined by the formula described below (Table 9). Similarly, also foreach of Compounds 6, 7, 9, 12, 13, and 15 to 20, an absolute value ofthe slope on the long wavelength side of the absorption peak in thewavelength region of 350 to 390 nm was determined from the absorptionspectrum. The absolute values are presented in Tables 2 and 4.|Slope on long wavelength side of absorption peak in wavelength regionof 350 to 390 nm|=|(Absorbance of peak end−absorbance of absorption peakin wavelength region of 350 to 390 nm)/(absorption wavelength of peakend−wavelength of absorption peak in wavelength region of 350 to 390nm)|

The absolute values of the slopes for Compounds 6 to 21 were all 0.030or more, and were larger than the absolute value of Compound 36 havingno thioether group (absolute value of the slope on the long wavelengthside of the absorption peak in the wavelength region of 350 to 390 nm:0.0219), while the peaks were sharp. Thus, it was suggested that thecompounds have an effect of suppressing yellowing in films, resinmembers, and particularly transparent resin members.

Furthermore, in regard to Compound 21, the molar absorption coefficientwas large, and when measurement was made at 100 μM, the absorbanceexceeded the measurement range. Therefore, as shown in Table 10, theabsorption peaks were measured at concentrations of 10, 25, and 50 μM,and the absolute value of the slope on the long wavelength side of theabsorption peak in the wavelength region of 350 to 390 nm was plottedagainst the concentration of the ultraviolet absorber. As shown in FIG.9, in a linear first-order relation, the absolute value of the slope at100 μM of Compound 21 was calculated by the equation of the graph(Y=0.0006X−0.0024). As a result, the slope of Compound 21 at 100 μM was0.0576, and this was larger than the slopes of other compounds. It wasconsidered that Compound 21 had a superior effect of suppressingyellowing in a film, a resin member, and particularly a transparentresin member.

From the absorption spectra of Compounds 6 to 21 and 36, the absorptionpeak (maximum absorption wavelength: λ_(max)) in the wavelength regionof 350 to 390 nm and the absorbance were read, and the molar absorptioncoefficient (maximum molar absorption coefficient: ε_(max)) of the peakwas determined by the following formula (Table 11).Molar absorption coefficient: ε_(max) (L/(mol·cm)=A: absorbance/[c:molar concentration (mol/L)×l: light path length of cell (cm)]

As a result, since Compounds 6 to 21 had thioether introduced thereinto,the molar absorption coefficients were as high as 17,000 or highercompared to Compound 36, and it was found that ultraviolet ray isefficiently absorbed by addition of small amounts of the compounds.Particularly, Compound 21 in a bis-form is considered to have a highermolar absorption coefficient than Compounds 6 to 20, and has superioreffects.

It was confirmed that all of the compounds of the present invention haveabsorption bands in the wavelength region of ultraviolet ray, andfunction as ultraviolet absorbers when added to films and resins.

It was confirmed that benzotriazole-based Compounds 6 to 21 of thepresent invention, in which the thioether group of (i-2) has beenintroduced into a benzotriazole group, has ultraviolet absorbency thatenables absorption of ultraviolet ray in the vicinity of 360 to 400 nm,which is a longer wavelength region even within the UV-A region (320 to400 nm) without cutting 420 to 500 nm (visible range), i.e. withoutyellowing, which ability is absent in Comparative Example 9 (Compound32) and 2-(2-hydroxy-3-t-butyl-5-methylphenyl)chlorobenzotriazole(Comparative Example 10, Compound 36, FIGS. 3 to 5) that has beenconventionally used as an ultraviolet absorber for long wavelengthabsorption. Furthermore, in Compounds 1, 2, 3 and 4, in which thethioether group of (i-2) has been introduced into the phenyl group on anitrogen atom of a benzotriazole-based compound, the absorption peak toprather significantly shifted to a short wavelength region (270 to 290nm), compared to Compound 32 of Comparative Example 9. That is, forbenzotriazole-based compounds, the UV absorption peak region wasadjustable by means of the position of the thioether group.

It was confirmed that owing to these characteristics, in Examples 71 to77 (FIGS. 10 to 16), when a small amount of the additive of the presentinvention is added to a plastic lens, absorption of wavelengths near 420nm or longer is suppressed while efficiently absorbing light having awavelength in the vicinity of 400 to 420 nm, which corresponds toharmful light, and thus an effect of suppressing yellowing of theplastic lens is obtained.

Also in regard to triazine-based Compounds 28 to 31, it was confirmedthat by having the substituent of (iv-2) introduced into the compounds,the absorption peak tops significantly shift to a long wavelength regioncompared to Comparative Example 13 (Compound 35), and the compounds canabsorb ultraviolet ray in the vicinity of 360 to 400 nm of a longwavelength region without cutting visible light (450 to 500 nm).Furthermore, it was confirmed that triazine-based Compounds 28 and 31each have an absorption peak even in a region of short wavelengthultraviolet ray (260 to 280 nm) in addition to the absorption peak topof a longer wavelength region (in the vicinity of 360 to 400 nm), andare capable of absorbing ultraviolet ray in a wide region.

2. Evaluation of Film

Compatibility (transparency) of the compounds of the present inventionwith films and resin members, and the effect of the compounds ofimparting a high refractive index were checked by methods describedbelow (Tables 1 to 8).

(Production of Acrylic Film)

The following three kinds of films having different film thicknesses, towhich the compounds of Examples 1 to 14 and 22 to 29, and ComparativeExamples 2 and 3 had been added, were produced.

A sample having a film thickness of 50 to 300 nm was produced byuniformly mixing 0.1 g of each of the compounds of Examples 1 to 14 and22 to 27 and Comparative Examples 2 and 3, with 0.1 g of an acrylicresin (manufactured by Mitsubishi Rayon Co., Ltd.) and 12 g ofchloroform, spin coating about 1 mL of the mixture on a glass substrateunder the conditions of 1,500 rpm and 20 seconds, and subsequentlyremoving the solvent for 2 hours in an oven at 45° C.

A sample having a film thickness of 301 to 1,500 nm was produced byuniformly mixing 0.1 g of each of the compounds of Examples 1 to 14 and22 to 27 and Comparative Examples 2 and 3, with 0.1 g of an acrylicresin and 4 g of chloroform, spin coating about 1 mL of the mixture on aglass substrate under the conditions of 1,500 rpm and 20 seconds, andsubsequently removing the solvent for 2 hours in an oven at 45° C.

A sample having a film thickness of 10 to 150 μm was produced byuniformly mixing 0.1 g of each of the compounds of Examples 1 to 14 and22 to 27 and Comparative Examples 2 and 3, with 0.1 g of an acrylicresin and 4 g of chloroform, subsequently concentrating chloroform toabout 2 to 3 g, dropping this on a slide glass, and then removing thesolvent for 2 hours in an oven at 45° C.

For Example 28 (film thickness: 50 to 300 nm, 301 to 1,500 nm, and 10 to150 μm) and Example 29 (film thickness: 50 to 300 nm, and 301 to 1,500nm), a similar operation was carried out by changing the blend of thecompound and the resin to 0.03 g and 0.07 g, respectively.

Furthermore, a film was produced by uniformly mixing 0.1 g of an acrylicresin with 4 g or 12 g of chloroform without adding an additive, andperforming an operation similar to that described above (ComparativeExample 1).

(Production of Urethane Film)

0.022 g of an isocyanate (HC-210 manufactured by Nippon PolyurethaneIndustry Co., Ltd.), 0.078 g of a polyol (ON-H37 manufactured by NipponPolyurethane Industry Co., Ltd.), and 0.1 g of each of the compounds ofExamples 1, 3 to 13, 22 and 24 to 27, and Comparative Example 2 wereuniformly mixed with 12 g of chloroform for a sample having a filmthickness of 50 to 300 nm, or with 4 g of chloroform for a sample havinga film thickness of 301 to 1,500 nm, and about 1 mL of the mixture wasspin coated on a glass substrate under the conditions of 1,500 rpm and20 seconds. Subsequently, chloroform was removed therefrom in an oven at45° C., and then the sample was heated for 3 hours at 100° C. Thus, aurethane film was produced.

A sample having a film thickness of 10 to 150 μm was produced byuniformly mixing 0.1 g of each of the compounds of Examples 4, 5, 8 and26 and Comparative Example 2, 0.022 g of an isocyanate, 0.078 g of apolyol, and 4 g of chloroform, subsequently concentrating about 2 to 3 gof chloroform, dropping this on a slide glass, subsequently removing thesolvent for 2 hours in an oven at 45° C., and then heating the samplefor 3 hours at 100° C.

For Example 28 (film thickness: 50 to 300 nm, 301 to 1,500 nm, and 10 to150 μm), the blend of the compound and the resin was changed to 0.03 gand 0.07 g (isocyanate 0.015 g, polyol 0.055 g), and an operationsimilar to that described above was carried out.

Furthermore, 0.022 g of an isocyanate, 0.078 of a polyol, and 4 g or 12g of chloroform were uniformly mixed without adding an additive, and anoperation similar to that described above was carried out. Thus, a filmwas produced (Comparative Example 1).

(Production of Thiourethane Film)

0.430 g of Compound 6, 0.1 g of ZELEC UN manufactured by Stepan Company,0.04 g of dibutyltin dichloride, and 50.8 g of a mixture of2,5-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane and2,6-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane were introduced into aflask, and the mixture was completely dissolved by stirring for 1 hourat 25° C. Subsequently, 22.4 g of pentaerythritoltetrakis(3-mercaptopropionate) and 26.8 g of1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane were added to the mixedliquid, and the resultant was mixed for 30 minutes at 25° C. Compound 6in the preparation liquid was included at a proportion of 0.430% byweight with respect to the total weight of polymerizable compounds.

This preparation liquid was subjected to degassing for one hour at 0.3mmHg or lower, and filtration was performed using a 5-μm PTFE filter.The preparation liquid was poured into a mold die formed from a glassmold for flat plate having a center thickness of 2 mm and a diameter of80 mm and a tape. This mold was slowly heated from 25° C. to 130° C.,maintained at 130° C. for 2 hours, and then cooled to room temperature.The time taken from the initiation of temperature increase to coolingwas 18 hours. After completion of polymerization, a molded product thusobtained was released from the mold, and annealing was performed for 2hours at 130° C.

Furthermore, thiourethane films were obtained by a method similar tothat used for Compound 6, except that instead of Compound 6, theultraviolet absorber to be added was changed to 0.472 g of Compound 7,0.490 g of Compound 8, 0.533 g of Compound 9, 0.555 g of Compound 10,0.651 g of Compound 11, 0.580 g of Compound 12, and 0.600 g of Compound13, respectively, while the same molar concentration was used.

In the thiourethane film to which Compound 13 was added, crystals wereprecipitated out, and clouding occurred; however, the thiourethane filmsto which Compounds 6 to 12 were added were transparent without havingcrystals precipitated out.

(Production of Polyethylene Terephthalate Film: PET)

For samples to which the additive was added at a proportion of 5 wt %, afilm having a thickness of 20 to 200 μm was produced by kneading 0.0418g of polyethylene terephthalate chips with 0.0022 g of each compound ofCompounds 1, 3, 5 to 13, 25 and 28 (Examples 6 to 13 and 30 to 35) andCompounds 32, 33 and 35 (Comparative Examples 6 to 8) at 280° C.,dropping this mixture on a slide glass substrate, quickly spreading themixture thereon, and air-cooling the mixture.

For samples to which the additive was added at a proportion of 10 wt %,a film having a thickness of 20 to 200 μm was produced by kneading0.0450 g of polyethylene terephthalate chips with 0.005 g of eachcompound of Compounds 1, 3, 5 to 13, 25 and 28 (Examples 6 to 13 and 30to 35) and Compounds 32, 33 and 35 (Comparative Examples 6 to 8) at 280°C., dropping this mixture on a slide glass substrate, quickly spreadingthe mixture thereon, and air-cooling the mixture.

For samples to which the additive was added at a proportion of 20 wt %,a film having a thickness of 20 to 200 μm was produced by kneading0.0352 g of polyethylene terephthalate chips with 0.0088 g of eachcompound of Compounds 1, 3, 5, 8, 25 and 28 (Examples 30 to 35) andCompounds 32, 33 and 35 (Comparative Examples 6 to 8) at 280° C.,dropping this mixture on a slide glass substrate, quickly spreading themixture thereon, and air-cooling the mixture.

For samples to which the additive was added at a proportion of 30 wt %,a film having a thickness of 20 to 200 μm was produced by kneading0.0566 g of polyethylene terephthalate chips with 0.0244 g of eachcompound of Compounds 1, 3, 5, 8, 25 and 28 (Examples 30 to 35) andCompounds 32, 33 and 35 (Comparative Examples 6 to 8) at 280° C.,dropping this mixture on a slide glass substrate, quickly spreading themixture thereon, and air-cooling the mixture.

Furthermore, a film having a thickness of 20 to 200 μm was produced bymelting 0.045 g of polyethylene terephthalate chips without adding anyadditive, and performing an operation similar to that described above(Comparative Examples 1 and 5).

(Production of Polystyrene Film: PS)

Films having a film thickness of 10 to 50 μm, to which the compounds ofExamples 6 to 13, 15 to 18, and 20 had been added, were produced by theprocedure described below.

A film was produced (50 wt %) by uniformly mixing 0.1 g of each of thecompounds of Examples 6 to 13, 15 to 18 and 20, 0.1 g of a polystyreneresin (Kanto Chemical Co., Inc.), and 4 g of chloroform, subsequentlyconcentrating about 2 to 3 g of chloroform, dropping 50 μL of thisconcentrate on a slide glass, and then removing the solvent for 2 hoursin an oven at 45° C.

Furthermore, for Compounds 19 and 21, a film was produced by performingan operation similar to that described above, by uniformly mixing ablend (10 wt %) of 0.0111 g of Compounds 19 or 21, 0.1 g of apolystyrene resin (Kanto Chemical Co., Inc.), and 2 g of chloroform. Fora blank film of Comparative example 1, a film was produced by performingan operation similar to that described above, by uniformly mixing 0.1 gof a polystyrene resin and 4 g of chloroform without adding any additivethereto.

(Production of Polycarbonate Film: PC)

Films having a film thickness of 10 to 50 μm, to which the compounds ofExamples 6 to 13, 15 to 18, and 20 had been added, were produced by theprocedure described below.

A film was produced (40 wt %) by uniformly mixing 0.0667 g of each ofthe compounds of Examples 6 to 13, 15 to 18, and 20, 0.1 g of apolycarbonate resin (Kanto Chemical Co., Inc.), and 4 g of chloroform,subsequently concentrating about 2 to 3 g of chloroform, dropping 25 μLof this on a slide glass, and removing the solvent for 2 hours in anoven at 45° C.

In regard to Compound 19, a film was produced by uniformly mixing ablend of 0.011 g of Compound 19, 0.1 g of a polycarbonate resin (KantoChemical Co., Inc.), and 2 g of chloroform (10 wt %). In regard toCompound 21, a film was produced by uniformly mixing a blend of 0.025 gof Compound 21, 0.1 g of a polycarbonate resin (Kanto Chemical Co.,Inc.), and 4 g of chloroform (20 wt %). A blank film of ComparativeExample 1 was produced by uniformly mixing 0.1 g of a polycarbonateresin and 4 g of chloroform without adding an additive, and performingan operation similar to that described above.

(Production of Urea Resin Film)

Films having a film thickness of 40 to 80 μm, to which Compounds ofExamples 6 to 13 were added, were produced by the procedure describedbelow.

1 mL of a 37 wt % formaldehyde solution, 0.25 g of urea, and 0.16 g ofammonium acetate were dissolved, and thus a monomer solution wasproduced. Next, 0.0007 g of each of the compounds of Examples 6 to 13was dissolved in 0.2 mL of THF, and the solution was uniformly mixedwith 0.1 mL of the monomer solution. 0.3 ml of the mixture was appliedon a slide glass having a size of 1.5×1.5 cm. Then, this slide glass wasplaced in an oven, and temperature was raised from room temperature to1500° C. over 30 minutes. Subsequently, the applied mixture was allowedto react for 5 hours at 150° C., and thus a film was produced.

Furthermore, a blank film for comparison was produced by uniformlymixing 0.1 mL of the monomer solution with 0.2 mL of THF without addingan additive, and performing an operation similar to that described above(Comparative Example 1).

(Production of Melamine Resin Film)

Films having a film thickness of 10 to 50 μm, to which the compounds ofExamples 6 to 13 were added, were produced by the procedure describedbelow.

To 5.15 g of a formaldehyde solution that had been conditioned to pH 7.5with sodium hydroxide, 1 g of melamine and 24.60 g of water were added,and the mixture was allowed to react under heating. Thus, ahexamethylolmelamine solution was produced. Next, 0.0057 g of each ofthe compounds of Examples 6 to 13 was dissolved in 0.1 mL of THF, andthe solution was uniformly mixed with 0.2 ml of the hexamethylolmelaminesolution. 0.3 mL of the mixture was applied on a slide glass having asize of 1.5×1.5 cm. Then, this slide glass was placed in an oven, andtemperature was raised from room temperature to 150° C. over 30 minutes.Subsequently, the applied mixture was allowed to react for 5 hours at150° C., and thus a film was produced.

Furthermore, a blank film for comparison was produced by uniformlymixing 0.2 ml of the monomer solution with 0.1 ml of THF without addingan additive, and performing an operation similar to that described above(Comparative Example 1).

(Production of Acrylic Melamine Resin Film)

Films having a film thickness of 100 to 150 μm, to which the compoundsof Examples 6 to 13 were added, were produced by the procedure describedbelow.

0.0045 g of each of the compounds of Examples 6 to 13 was dissolved in0.1 mL of THF such that when the solution was produced into a film, theconcentration of the compound would be 10 wt %, and the solution wasuniformly mixed with 0.1 mL of a baking and drying type top coat paint(baking and drying type top coat (acrylic melamine): ACRYCITE UB-63CLEAR manufactured by Saito Paint Co., Ltd.). 0.2 mL of the mixture wasapplied on a slide glass having a size of 1.5×1.5 cm. Then, this slideglass was placed in an oven, and temperature was raised from roomtemperature to 150° C. over 30 minutes. Subsequently, the appliedmixture was allowed to react for 2 hours at 150° C., and thereby, anacrylic melamine resin film containing 10 wt % of an additive wasobtained.

Furthermore, a blank film for comparison was produced by uniformlymixing 0.1 mL of an acrylic melamine monomer with 0.1 mL of THF withoutadding an additive, and performing an operation similar to thatdescribed above (Comparative Example 1).

(1) External Appearance

The external appearance of a film was visually observed, and wasevaluated according to the following criteria.

Evaluation criteria (acrylic film, urethane film, and thiourethane film)

◯: Transparent without cloudiness.

x: Cloudiness is observed, and transparency is poor.

Evaluation Criteria (PET Film)

⊙: Having equivalent transparency compared to the blank of ComparativeExample.

◯: Having very slight cloudiness compared to the blank of ComparativeExample.

Δ: Having slight cloudiness compared to the blank of ComparativeExample.

x: Having obvious cloudiness compared to the blank of ComparativeExample.

Evaluation Criteria (PS Film)

◯: Having equivalent transparency compared to the blank of ComparativeExample.

Δ: Having slight cloudiness compared to the blank of ComparativeExample.

x: Having obvious cloudiness compared to the blank of ComparativeExample.

Evaluation Criteria (PC Film)

◯: Having equivalent transparency compared to the blank of ComparativeExample.

Δ: Having slight cloudiness compared to the blank of ComparativeExample.

x: Having obvious cloudiness compared to the blank of ComparativeExample.

Evaluation Criteria (Urea Resin Film)

◯: Transparent without precipitation of crystals.

Δ: Slight precipitation of crystals is observed, but transparent.

x: Precipitation of crystals is observed, and transparency is poor.

Evaluation Criteria (Melamine Resin Film)

◯: Transparent without precipitation of crystals.

x: Precipitation of crystals is observed, and transparency is poor.

Evaluation Criteria (Acrylic Melamine Resin Film)

◯: Transparent without precipitation of crystals.

Δ: Partial precipitation of crystals is observed, and transparency ispoor.

x: Precipitation of crystals is generally observed, and transparency ispoor.

The conditions for the alkyl chain, melting point, and thesulfur-containing group of the additive were in agreement, andtherefore, compatibility of the thermoplastic resins with an acrylicfilm (transparentization) was enhanced.

Regarding the alkyl chain, the films having a thickness of 50 to 300 nmbecame transparent, for compounds a having thiol group, when the numbersof carbon atoms of the functional groups —(CH₂)_(n)—SH and —(CH₂)_(n)CH₃were respectively 9 or less (Compounds 1 and 22); and for compoundshaving a thioether group, when the numbers of carbon atoms of thefunctional groups —(CH₂)_(n)—S—, —S—(CH₂)_(n)—S—, and —S—(CH₂)_(n)CH₃were respectively 17 or less (Compounds, 3, 4, 6 to 10, 12 to 14, and 23to 29). Furthermore, in regard to compounds having a thioether group,generally, when compounds having the aforementioned number of carbonatoms of 8 or less were used, even thicker films having a film thicknessof 301 to 1,500 nm also became transparent (Compounds 3, 4, 7, 8, 12,14, and 23 to 27). That is, it was confirmed that the number of carbonatoms is important for compatibility with a resin (transparency), and acompound having an alkyl chain with a length of from a medium chain to ashort chain tends to have enhanced phase dissolution properties(transparentization).

In regard to benzotriazole, benzophenone, and salicylate-basedcompounds, generally, there was a correlation between the melting pointand the compatibility with a resin, in addition to the correlation withthe alkyl chain as described above. Thus, when melting point waslowered, phase dissolution properties (transparentization) wereenhanced. Compounds having a melting point of 91° C. or lower (Compounds1, 3, 4, 5, 6 to 10, 12 to 14, and 22 to 27) generally transparentizedfilms having film a thickness of 50 to 300 nm, despite high proportionsof addition of 50%. Furthermore, compounds having a melting point ofbelow 70° C. (Compounds 1, 3, 4, 5, 7, 8, 9, 14 and 23 to 27)transparentized thicker films having a thickness of 301 to 1,500 nm, andcompounds having a melting point of 35° C. or lower (liquid at normaltemperature) (Compounds 1, 3, 4 and 24 to 27) realizedtransparentization even at a larger thickness of 10 to 150 μm.

However, in acrylic films having a thickness of 10 to 150 μm, otherCompounds 3 and 4 having a melting point of 35° C. or lower and having asulfur-containing group transparentized an acrylic film, whereasCompound 5 having no sulfur-containing group caused clouding in anacrylic film despite having a melting point of 25° C. or lower.

On the other hand, Compounds 6 to 10, 12 and 13 obtained by introducinga sulfur-containing group into2-(2-hydroxy-3-t-butyl-5-methylphenyl)-chlorobenzotriazole (ComparativeExample 10, Compound 36) as a raw material, transparentized urethanefilms having a film thickness of 50 to 300 nm, whereas2-(2-hydroxy-3-t-butyl-5-methylphenyl)-chlorobenzotriazole (ComparativeExample 10, Compound 36) that did not have a sulfur-containing groupcaused clouding. Thus, it was suggested that introduction of asulfur-containing group was one of requirements for compatibility(transparency) with a resin.

After all, Compound 33 having no sulfur-containing group has a lowmelting point of 47° C. to 48° C. compared to Compound 22 having amelting point of 91° C. and Compound 23 having a melting point of 60.5°C. to 69° C.; however, while Compounds 22 and 23 transparentized acrylicfilms having a film thickness of 50 to 300 nm, Compound 33 clouded anacrylic film. That is, it was suggested that not only the melting point,but also the presence of a sulfur-containing group enhance phasedissolution properties (transparentization) for a resin.

Furthermore, Compound 2 (number of carbon atoms: 10) having a thiol hasa melting point of 25° C. or lower, and Compound 11 (number of carbonatoms: 18) having a thioether has a melting point of 73° C. to 83° C.However, despite that the melting point was 91° C. or lower, acrylicfilms having a thickness of 50 to 300 nm were not transparentized. Thatis, it is speculated that it is also important to satisfy therequirements of both the melting point and the number of carbon atoms,and since Compounds 2 and 11 have 10 carbon atoms and 18 carbon atoms,respectively, which are larger numbers of carbon atoms than the numberof carbon atoms defined above (compound having a thiol group: number ofcarbon atoms being 9 or less, compound having a thioether group: numberof carbon atoms being 17 or less), and the condition for the number ofcarbon atoms is not satisfied, the acrylic films were nottransparentized.

Urethane resins, which are thermosetting resins, also had the sametendency, and exhibited satisfactory transparency as a result of theeffects of the alkyl chain, melting point, and sulfur-containing groupof the additives of the present invention.

Also for Compounds 1, 3, 8, 25 and 28 of the present invention, theadditives of the present invention having a sulfur-containing groupintroduced thereinto exhibited satisfactory heat resistance (5% weightreduction temperature: Compound 8: 295° C., Compound 5: 249° C.) andsatisfactory transparency with high compatibility with PET resins, whichare thermoplastic resins, at a heated molding temperature of 280° C.under the conditions of high concentration and a high film thickness of20 to 200 μm, compared to Compounds 5, 32, 33 and 35, as a result of theeffects of the alkyl chain, melting point, and sulfur-containing groupas described above (Table 8).

In regard to Compounds 6 to 13 having a group of Formula (i-2) forR^(7a) or R^(8a) of Formula (I), for an evaluation (Tables 2 and 3) ofcompatibility (transparency) with the various resins indicated in Tables2 and 3 (acrylic (50 to 300 nm, 301 to 1,500 nm, and 10 to 150 μm),urethane (50 to 300 nm, and 301 to 1,500 nm), thiourethane, PET (5, 10wt), PS, PC, urea, melamine, and acrylic melamine), the number of themost satisfactory ratings (acrylic, urethane, thiourethane, PS, PC,urea, melamine, and acrylic melamine: ◯, PET: ⊙), and the number ofpoorest ratings (acrylic, urethane, thiourethane, PET, PS, PC, urea,melamine, and acrylic melamine: x) were counted, and comprehensivecompatibility of the various compounds with resins (transparency) wasevaluated according to the criteria of Table 12. The results arepresented in Table 13.

As a result, compounds that obtained a rating of 1 or higher werecompounds having a number of carbon atoms of R^(13a) of 1 to 18 andhaving a melting point of 91° C. or lower (Compounds 6, 7, 8, 9, 10, 11,12 and 13); compounds that obtained a rating of 2 or higher werecompounds having a number of carbon atoms of R^(13a) of 1 to 12 andhaving a melting point of 91° C. or lower (Compounds 6, 7, 8, 9, 10, 12and 13); compounds that obtained a rating of 3 or higher were compoundshaving a number of carbon atoms of R^(13a) of 1 to 10 and having amelting point of 91° C. or lower (Compounds 6, 7, 8, 9 and 12), orcompounds having a number of carbon atoms of R^(13a) of 1 to 12, havinga melting point of 91° C. or lower, and having a methyl group and at-butyl group as the substituents for R^(2a) and R^(4a) (Compounds 6, 7,8, 9 and 10); compounds that obtained a rating of 4 or higher werecompounds having a number of carbon atoms of R^(13a) of 1 to 12, havinga melting point of 91° C. or lower, and having a methyl group and at-butyl group as the substituents for R^(2a) and R^(4a) (Compounds 6, 7,8, 9 and 10); and compounds that obtained a rating of 5 or higher werecompounds having a number of carbon atoms of R^(13a) of 4 to 10, havinga melting point of 91° C. or lower, and having a methyl group and at-butyl group as the substituents for R^(2a) and R^(4a) (Compounds 6, 7,8 and 9); and compounds that obtained a rating of 6 or higher werecompounds having a number of carbon atoms of R^(13a) of 6 to 10, havinga melting point of below 70° C., and having a methyl group and a t-butylgroup as the substituents for 2a and 4a (Compounds 7, 8 and 9).Compatibility (transparency) with a resin serving as a matrix wasdependent not only on any one of the number of carbon atoms of the alkylof Formula (i-2) in the benzotriazole skeleton of Formula (I) as thestructure of the additive, and the melting point of the compound, butwas dependent on both of them (Compound 12 (number of carbon atoms: 8,melting point: 80° C. to 81° C.) having a number of carbon atoms of 10or less but having a melting point of 70° C. or higher: Rating 3; andCompound 13 (number of carbon atoms: 12, melting point: 64° C. to 66°C.) having a melting point of below 70° C. but having a number of carbonatoms of 10 or more: Rating 2, indiscriminately did not obtainsatisfactory ratings).

Furthermore, similarly to the number of carbon atoms of R^(13a) Compound8 in which the substituents for R^(1a) to R^(5a) are different (numberof carbon atoms of R^(13a): 8, substituents for 2a and 4a: methyl group,t-butyl group) and Compound 12 (number of carbon atoms of R^(13a): 8,substituents for R^(2a), R^(4a): t-butyl group, t-butyl group) arecompared, and Compound 10 (number of carbon atoms of R^(13a): 12,substituents for R^(2a), R^(4a): methyl group, t-butyl group) andCompound 13 (number of carbon atoms of R^(13a): 12, substituents forR^(2a), R^(4a): t-butyl group, t-butyl group) are compared, Compound 8showed satisfactory compatibility (transparency) in PET, which is athermoplastic resin, and in urea, melamine and acrylic melamine resin,which are thermosetting resins, compared to Compound 12; and Compound 10showed satisfactory compatibility (transparency) in thiourethane andPET, which are thermoplastic resins, and in melamine and acrylicmelamine, which are thermosetting resins, compared to Compound 13 (FIG.17). Compound 8 and Compound 10 also had higher points for theabove-described ratings. That is, in regard to compatibility(transparency) with a resin, compounds having a methyl group and at-butyl group as the substituents for R^(2a) and R^(4a) generally tendto be satisfactory, and compounds having a number of carbon atoms ofR^(13a) of 12 or less (Compounds 6, 7, 8, 9 and 10), even compoundshaving the number of carbon atoms of 4 to 10 (Compounds 6, 7, 8 and 9),and particularly Compounds 7, 8 and 9 having the number of carbon atomsof 6 to 10, exhibited satisfactory compatibility (transparency) with allresins, irrespective of being thermosetting resins or thermoplasticresins, such as acrylic, urethane, thiourethane, PET, PS, PC, urea, andmelamine.

Furthermore, Compounds 15 to 21 having a thioether group, which have abranched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbongroup, an alkene group-containing aliphatic hydrocarbon group, anaromatic group, an oxygen-containing aliphatic hydrocarbon group, andthe like, also exhibited compatibility (transparency) with PS and PC,and thus the effects of the introduction of a sulfur-containing group,the melting point and the like were suggested.

(2) Film Thickness

The film thickness was measured at a cross-section generated by cuttinga film, using a tabletop microscope (MINISCOPE TM3000 manufactured byHitachi High-Technologies Corp.), or the reflectance of a film wasmeasured using a reflectance meter (USPM-RU manufactured by OlympusCorp.), and the film thickness was obtained by analyzing the reflectancewaveform thus obtained, through fitting using Hartmann dispersionformula.

(3) Refractive Index The refractive index of a film was determined bymeasuring from the single-surface reflectance (λ=589 nm) (Tables 1, 2,5, 6 and 7).

Acrylic resin films to which the compounds of the present invention wereadded (Compounds 1, 3, 4, 5, 8, 10, 14, 22, 23, 24, 25, 26, 27 and 28:refractive indices 1.5178 to 1.5914) acquired higher refractive indicesthan the non-added film of Comparative Example 1 (1.4985). Compared toCompound 5 having no sulfur-containing group, Compounds 1, 3, 4, 8, 10and 14 each having a sulfur-containing groups had high refractiveindices, and thus an effect of the present invention of imparting a highrefractive index provided by the compounds of the present inventionhaving sulfur-containing groups was suggested.

From these results, it was confirmed that the compounds of Examples cutthe wavelengths in the ultraviolet region in the vicinity of 250 to 400nm, and transmit the wavelengths of 450 to 500 nm (visible range).Particularly, it was confirmed that the compounds of Examples haveexcellent ultraviolet absorbency for 315 to 400 nm (UV-A region), whichmay affect photodegradation of organic substances, and cut ultravioletray even up to the region near 400 nm. Therefore, the additives of thepresent invention can prevent deterioration or discoloration of a resinserving as a matrix, and are useful. Furthermore, an effect ofincreasing the refractive index of a resin film was also recognized. Itwas also confirmed that even if the additive is added in an amount of0.4 wt % to 50 wt % with respect to the sum of the amounts of the resinand the additive, the film remains transparent without discoloration,and that the compounds of Examples have high solubility in a resin andcan be used in high concentrations while maintaining transparency.

TABLE 1 Exam- ple or Acrylic Com- Additive 50~300 nm para- Ap- Refrac-301~1500 nm tive pear- Refrac- tive Film Exam- Com- ance Melting tiveAp- Film index Ap- thick- ple pound (35° point index pear- thick- (589pear- ness No. No. Structure C.) ° C. (20° C.) ance ness nm) ance (nm)Com- No additive ∘  72 1.7985 ∘ 1050 para- tive Exam- ple 1 Exam- ple 1 1

Liquid ≤25 1.6043 ∘  78 1.5378 ∘  981 Exam- ple 2  2

Liquid ≤25 1.5980 x  78 — x  761 Exam- ple 3  3

Liquid ≤25 1.6138 ∘ 295 1.5677 ∘ 1125 Exam- ple 4  4

Liquid ≤25 1.6131 ∘ 210 1.5657 ∘ 1251 Exam- ple 5  5

Liquid ≤25 1.5735 ∘  74 1.5288 ∘  876 Com- para- tive Exam- ple 2 32

Solid 75-76.5 1.595 x  77 — x  856 Acrylic Urethane 10~150 μm 50~300 nm10~150 μm Film Film 301~1500 nm Film Example or thick- thick- Filmthick- Comparative ness ness thickness ness Example No. Appearance (μm)Appearance (nm) Appearance (nm) Appeance (μm) Comparatiave ∘ 29 ∘ 179 ∘677 ∘ 16 Example 1 Example 1 ∘ 21 ∘ 116 ∘ 553 — — Example 2 x 28 — — — —— — Example 3 ∘ 27 ∘ 258 ∘ 383 — — Example 4 ∘ 75 ∘ 191 ∘ 591 ∘ 44Example 5 x 37 ∘ 241 ∘ 345 x 29 Comparative x 29 x 121 x 331 x 25Example 2

TABLE 2 Resin Additive Absolute value of slope on longer wave- lengthside of absorp- 5% tion weight peak in reduc wave- tion Melt- Refrac-length tem- Example or Com- Ap- ing tive region of pera- Comparativepound pear- point index 350 to ture Example No. No. Structure ance ° C.(20° C.) 390 nm (° C.) Comparative No additive Example 1 Example 6  6

Solid 87 — 0.0369 260 Example 7  7

Solid 69 — 0.0363 277 Example 8  8

Solid 50~63 — 0.0355 294 Example 9  9

Solid 68~69 — 0.0367 303 Exampe 10 10

Solid 70~72 — 0.0358 315 Example 11 11

Solid 73~83 — 0.0365 305 Example 12 12

Solid 80~81 — 0.0372 294 Example 13 13

Solid 64~66 — 0.0376 307 Example 14 14

Solid 40~45 1.6019 (46° C.) 0.0345 293 Exam- Acrylic ple or Additiveconcentration: 50 wt % Urethane Com- 50~300 nm Additive concentration:50 wt % Thiour- para- Refrac- 301~1500 nm 10~150 μm 50~300 nm 301~1500nm 10~150 μm ethane tive Film tive Film Film Film Film Film — Exam- Ap-thick- index Ap- thick- Ap- thick- Ap- thick- Ap- thick- Ap- thick- 2 mmple pear- ness (589 pear- ness pear- ness pear- ness pear- ness pear-ness Appear- No. ance (nm) nm) ance (nm) ance (μm) ance (nm) ance (nm)ance (μm) ance Com- ∘  72 1.4985 ∘ 1050 ∘ 29 ∘ 179 ∘  677 ∘ 16 ∘ para-tive Exam- ple 1 Exam- ∘ 261 — x 1231 x 35 ∘ 228 x 1050 — — ∘ ple 6Exam- ∘ 252 — ∘ 1209 x 72 ∘ 264 x 1348 — — ∘ ple 7 Exam- ∘ 204 1.5664 ∘1348 x 21 ∘ 288 ∘ 1100 x 20 ∘ ple 8 Exam- ∘ 263 — ∘ 1343 x 40 ∘ 260 ∘1301 — — ∘ ple 9 Exam- ∘ 224 1.5377 x  943 x 42 ∘ 224 ∘ — — — ∘ ple 10Exam- x  75 — x 1236 x 92 x  75 x — — — ∘ ple 11 Exam- ∘ 267 — ∘ 1208 x81 ∘ 229 ∘ 1020 — — ∘ ple 12 Exam- ∘ 270 — x 1280 x 55 ∘ 240 ∘  996 — —x ple 13 (Crystals precipi- tated Exam- ∘ 240 1.5531 ∘ 1354 x 86 — — — —— — — ple 14

TABLE 3 PET PS Additive Additive Additive concentration: concentrationconcen- 5 wt % 10 wt % tration: Example or 20~200 μm 50 wt % ComparativeCom- Film Film 10~50 μm Example pound thickness thickness Appear- No.No. Structure Appearance (μm) Appearance (μm) ance (μm) Comparative Noadditive ⊚ 104 ⊚  29 ◯ 14 Example 1 Example 6  6

⊚ 128 ◯ 127 ◯ 47 Example 7  7

⊚ 114 ◯  84 ◯ 35 Example 8  8

⊚ 110 ◯ 110 ◯ 22 Example 9  9

⊚ 120 ◯ 136 ◯ 38 Example 10 10

⊚ 114 X  64 Δ 41 Example 11 11

◯  89 X  97 X 34 Example 12 12

◯ 194 X  96 ◯ 28 Example 13 13

◯ 115 X  83 Δ 29 Acrylic PC Urea Melamine melamine Additive AdditiveAdditive Additive concentration: concentraion: concentraion:concentration 40 wt % 1 wt % 30 wt % 10 wt % 10~50 μm 40~80 μm 10~50 μm100~150 μm Film Film Film Film thickness thickness thickness Appear-thickness No. Appearance (μm) Appearance (μm) Appearance (μm) ance (μm)Comparative ◯ 13 ◯ 75 ◯ 19 ◯ 115 Example 1 Example 6 ◯ 19 ◯ 58 ◯ 46 ◯111 Example 7 ◯ 17 ◯ 46 ◯ 26 ◯ 125 Example 8 ◯ 39 ◯ 60 ◯ 27 ◯ 129Example 9 ◯ 18 ◯ 54 ◯ 24 ◯ 119 Example 10 Δ 23 Δ 46 ◯ 45 ◯ 127 Example11 X 16 X (Crystals 54 X (Crystals 41 X 114 precipitated) precipitated)Example 12 ◯ 19 X (Crystals 72 X (Crystals 15 Δ 128 precipitated)precipitated) Example 13 Δ 25 X (Crystals 55 X (Crystals 17 X 113precipitated) precipitated)

TABLE 4 Resin Additive Example or Re- Comparative Com- Appear- Meltingfractive Example pound ance point index No. No. Structure (35° C.) ° C.(20° C.) Comparative No additive Example 1 Example 15 15

Solid 81~82 — Example 16 16

Solid 141~142 — Example 17 17

Solid 162~167 — Example 18 18

Solid 140~142 — Example 19 19

Solid 129~132 — Example 20 20

Solid 71~75 — Example 21 21

Solid 187~190 — Resin Additive Absolute value of slope on longer wave-length side of absorption PS PC peak in Additive Additive wave-concentration: 50 wt % concentration: 40 wt % length 5% weight 10~50 μm10~50 μm Example or region of reduction Film Film Comparative 350 to 390temperature thickness thickness Example No. nm (° C.) Appearance (μm)Appearance (μm) Comparative ∘ 14 ∘ 13 Example 1 Example 15 0.0359 259 ∘25 ∘ 16 Example 16 0.0359 283 ∘ 16 Δ 24 Example 17 0.0321 252 ∘ 35 Δ 22Example 18 0.0373 293 ∘ 29 Δ 28 Example 19 0.0340 287 ∘ 17 ∘ 19 (10 wt%) (10 wt %) Example 20 0.0324 281 x 32 ∘ 13 Example 21 0.0576 329 Δ 18∘ 15 (10 wt %) (20 wt %)

TABLE 5 Additive 5% weight reduc- tion Example or Refrac- tem-Comparative Com- Appear- Melting tive pera- Example pound ance pointindex ture No. No. Structure (35° C.) (° C.) (20° C.) (° C.) Example 2222

Solid 91 — — Example 23 23

Solid 60.5~69 — 279 Example 24 24

Liquid 30~34 1.5940 (34° C.) 260 Example 25 25

Liquid ≤25 1.6151 — Comparative Example 3 33

Solid 47~48 1.547 249 Acrylic 50~300 nm Urethane Example or Refrac-301~1500 nm 10~150 μm 50~300 nm 301~1500 nm 10~150 μm Film tive FilmFilm Film Film Film Comparative Ap- thick- index Ap- thick- Ap- thick-Ap- thick- Ap- thick- Ap- thick- Example pear- ness (589 pear- nesspear- ness pear- ness pear- ness pear- ness No. ance (nm) nm) ance (nm)ance (μm) ance (nm) ance (nm) ance (μm) Example 22 ∘ 220 1.5910 x  987 x 22 ∘ 258 — — — — Example 23 ∘ 237 1.5627 ∘  893 x  87 — — — — — —Example 24 ∘  75 1.5914 ∘ 1231 ∘  20 ∘ 182 ∘ 330 — — Example 25 ∘ 2421.5364 ∘ 1081 ∘ 144 ∘ 278 ∘ 504 — — Comparative x  70 — x  821 x  21 — —— — — — Example 3

TABLE 6 Additive 5% weight reduc- tion Example or Refrac- tem-Comparative Com- Appear- Melting tive pera- Example pound ance pointindex ture No. No. Structure (35° C.) (° C.) (20° C.) (° C.) Example 2626

Liquid 25 1.58 — Example 27 27

Liquid 25 1.557 264 Comparative Example 4 34

Solid 191~192.5 1.52 249 Acrylic 50~300 nm Urethane Refrac- 301~1500 nm10~150 μm 50~300 nm 301~1500 nm 10~150 μm Example or Film tive Film FilmFilm Film Film Comparative Ap- thick- index Ap- thick- Ap- thick- Ap-thick- Ap- thick- Ap- thick- Example pear- ness (589 pear- ness pear-ness pear- ness pear- ness pear- ness No. ance (nm) nm) ance (nm) ance(μm) ance (nm) ance (nm) ance (μm) Example 26 ∘ 189 1.5477 ∘ 821 ∘ 129 ∘178 ∘ 680 ∘ 80 Example 27 ∘ 227 1.5340 ∘ 833 ∘ 114 ∘ 111 ∘ 507 — —Comparative — — — — — — — — — — — — — Example 4

TABLE 7 Acrylic Example Additive 50~300 nm or Refrac- Refrac- Compar-tive Film tive ative Com- Appear- Melting Index thick- index Examplepound ance point (20° Appear- ness (589 No. No. Structure (35° C.) ° C.C.) ance (nm) nm) Example 28 28

Solid 190~192 — ∘ 278 1.5178 Example 29 29

Solid 123.5~126 — ∘ 288 — Acrylic Urethane 301~1500 nm 10~150 μm 50~300nm 301~1500 nm 10~150 μm Film Film Film Film Film Example or thick-thick- thick- thick- thick- Comparative Appear- ness Appear- nessAppear- ness Appear- ness Appear- ness Example No. ance (nm) ance (um)ance (nm) ance (nm) ance (um) Example 28 ∘  805 x 28 ∘ 222 x 800 x 44Example 29 x 1456 — — — — — — — —

TABLE 8 Example or PET Comparative Compound 5 wt % 10 wt % 20 wt % 30 wt% Example No. No. Structural formula Appearance Appearance AppearanceAppearance Comparative PET only ⊙ ⊙ ⊙ ⊙ Example 5 Example 30  1

⊙ ⊙ Δ Δ Example 31  3

⊙ ⊙ Δ Δ Example 32  8

⊙ ⊙ Δ X Example 33  5

⊙ ◯ X X Comparative Example 6 32

⊙ ◯ X X Example 34 25

⊙ ⊙ Δ Δ Comparative Example 7 33

⊙ ◯ X X Example 35 28

⊙ ⊙ ◯ Δ Comparative Example 8 35

◯ Δ X X

TABLE 9 Absorbance of Absolute value of absorption slope on longer peakin wavelength side of wavelength region Absorption absorption peak in of350 to Absorbance of wavelength of wavelength region 390 nm peak endpeak end nm of 350 to 390 nm Compound 8 2.13704 0.00147 426.0 0.0365Compound 10 2.09328 0.00089 426.0 0.0358 Compound 11 2.08832 0.00909424.0 0.0365 Compound 14 2.05024 0.00023 425.5 0.0345 Compound 212.15433 0.00023 425.5 0.0368 Compound 36 1.52567 0.00517 423.0 0.0219*Compound 36: 2-(2-Hydroxy-3-t-butyl-5-methylphenol)-chlorobenzotriazole

TABLE 10 Wavelength of absorption peak in Absolute value of Absorbanceof wavelength region slope on longer absorption peak of 350 to 390 nmwavelength side of in wavelength Absorption (Maximum absorption peak inregion of 350 to Absorbance wavelength of absorption wavelength regionConcentration 390 nm of peak end peak end nm wavelength: λ_(max)) of 350to 390 nm 10 μM 0.21585 0.00013 427.5 367.0 0.00357 25 μM 0.7874 0.00343427.0 367.0 0.01307 50 μM 1.69356 0.00541 427.0 367.0 0.02814

TABLE 11 Wavelength of absorption peak in wavelength region of 350 to390 nm Molar absorption coefficient of peak (Maximum absorptiondescribed on left side (Maximum Molecular weight wavelength: λ_(max))molar absorption coefficient: ε_(max)) g/mol nm L/(mol · cm) Compound 6370 367.0 22200 Compound 7 398 367.0 22200 Compound 8 426 367.5 21400Compound 9 454 367.5 22300 Compound 10 482 367.5 20900 Compound 11 566367.0 20800 Compound 12 468 366.5 22400 Compound 13 523 366.5 22100Compound 14 500 366.0 20400 Compound 15 369 367.0 21100 Compound 16 396367.5 21100 Compound 17 353 375.0 17600 Compound 18 404 369.0 21500Compound 19 404 366.0 20100 Compound 20 357 364.0 19800 Compound 21 709367.0 43100 Compound 36 316 353.5 15300

TABLE 12 Evaluation 6 5 4 3 2 1 ◯ + ⊙ 10 or 9 or 7 or 7 or 3 or 1 ormore more more more more more X 2 or 3 or 3 or 4 or 7 or 11 or fewerfewer fewer fewer fewer fewer

TABLE 13 Number of carbon Compound atoms of ⊙ and No. Structure R^(13a)Melting point ◯ X Evaluation 6

4 87 9 3 5 7

6 69 10 2 6 8

8 50~63 11 1 6 9

10 68~69 11 1 6 10

12 70~72 7 3 4 11

18 73~83 1 11 1 12

8 80~81 7 4 3 13

12 64~66 3 7 2

3. Evaluation of Plastic Lens

(Production of Plastic Lens)

Resins respectively having the additives of the present invention andconventional ultraviolet absorbers added thereto were produced. In thefollowing Examples and Comparative Examples, the amount of addition ofeach ultraviolet absorber was adjusted such that the transmittance of420 nm of flat lenses having a thickness of 2 mm would have values asclose to one another as possible in the same type of resin material.

Example 71

0.49 g of Compound 8, 0.1 g of ZELEC UN manufactured by Stepan Company,0.04 g of dibutyltin dichloride, and 50.8 g of a mixture of2,5-bis(isocyanatomethyl)-bicyclo[2,2,1]heptane and2,6-bis(isocyanatomethyl)-bicyclo[2,2,1]heptane were introduced into aflask, and the mixture was stirred for one hour at 25° C. to completelydissolve. Subsequently, 22.4 g of pentaerythritoltetrakis(3-mercaptopropionate) and 26.8 g of1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane were added to thismixed liquid, and the mixture was mixed for 30 minutes at 25° C.Meanwhile, Compound 8 was included in the preparation liquid in anamount of 0.49% by weight with respect to the total weight ofpolymerizable compounds.

This preparation liquid was subjected to degassing for one hour at 0.3mmHg or less, and to filtration through a 5-μm PTFE filter. Thepreparation liquid was injected into a molding mold formed from a glassmold for flat plate having a center thickness of 2 mm and a diameter of80 mm and a tape. This mold was slowly heated from 25° C. to 130° C.,maintained at 130° C. for 2 hours, and then cooled to room temperature.The time taken from the initiation of temperature increase to coolingwas 18 hours. After completion of polymerization, the molded productthus obtained was released from the mold, and this flat lens wassubjected to annealing for 2 hours at 130° C.

Example 72

A flat lens having a thickness of 2 mm was obtained by a method similarto that used in Example 71, except that Compound 8 of Example 71 wasadded in an amount of 0.53 g (0.53% by weight with respect to the totalweight of polymerizable compounds).

Example 73

0.53 g of Compound 8 (0.53% by weight with respect to the total weightof polymerizable compounds), 0.1 g of ZELEC UN manufactured by StepanCompany, 0.2 g of dibutyltin dichloride, and 58.9 g ofdicyclohexylmethane-4,4′-diisocyanate were introduced into a flask, andthe mixture was stirred for one hour at 25° C. to completely dissolve.Subsequently, 41.1 g of a mixture including5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane as maincomponents was added to the mixed liquid, and the resulting mixture wasmixed for 30 minutes at 25° C.

A flat lens having a thickness of 2 mm was obtained by a method similarto that used in Example 71, except for the production of the preparationliquid.

Example 74

0.27 g of Compound 8 (0.27% by weight with respect to the total weightof polymerizable compounds), 0.1 g of ZELEC UN manufactured by StepanCompany, 0.006 g of dibutyltin dichloride, and 50.6 g of m-xylenediisocyanate were introduced into a flask, and the mixture was stirredfor one hour at 25° C. to completely dissolve. Subsequently, 49.4 g of amixture including5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane as maincomponents was added to the mixed liquid, and the resulting mixture wasmixed for 30 minutes at 25° C.

A flat lens having a thickness of 2 mm was obtained by a method similarto that used in Example 71, except for the production of the preparationliquid.

Example 75

0.23 g of Compound 8 (0.23% by weight with respect to the total weightof polymerizable compounds), 71 g of bis(β-epithiopropyl) sulfide, 23 gof sulfur, and 2.2 g of (2-mercaptoethyl) sulfide were introduced into aflask, and the mixture was stirred for 30 minutes at 60° C.Subsequently, 0.14 g of 2-mercapto-1-methylimidazole was introducedthereinto, and the mixture was subjected to degassing for 10 minutes at0.3 mmHg or less. Subsequently, the mixture was stirred for 120 minutesat 60° C., and then the mixture was cooled to 30° C. for 40 minutes. Tothe solution thus obtained, a solution obtained by dissolving 0.012 g oftriethylbenzylammonium chloride and 0.01 g of dibutyltin dichloride in3.8 g of (2-mercaptoethyl) sulfide was added dropwise, and the mixturewas degassed for 20 minutes at 0.3 mmHg or less. This solution wasfiltered through a 5-μm PTFE filter, and was injected into a moldingmold formed from a glass mold for flat plate having a center thicknessof 2 mm and a diameter of 80 mm and a tape. This mold was slowly heatedfrom 25° C. to 110° C., maintained at 1100° C. for 2 hours, and thencooled to room temperature. The time taken from the initiation oftemperature rise to cooling was 18 hours. After completion ofpolymerization, the molded product thus obtained was released from themold, and this flat lens was subjected to annealing for 2 hours at 110°C.

Example 76

A flat lens having a thickness of 2 mm was obtained by a method similarto that used in Example 71, except that Compound 8 of Example 71 waschanged to Compound 10, and Compound 10 was added in an amount of 0.56 g(0.56% by weight with respect to the total weight of polymerizablecompounds).

Example 77

A flat lens having a thickness of 2 mm was obtained by a method similarto that used in Example 71, except that Compound 8 of Example 71 waschanged to Compound 14, and Compound 14 was added in an amount of 0.58 g(0.58% by weight with respect to the total weight of polymerizablecompounds).

Comparative Example 14

A flat lens having a thickness of 2 mm was obtained by a method similarto that used in Example 71, except that Compound 8 of Example 71 waschanged to 2-(2-hydroxy-3-t-butyl-5-methylphenyl)-chlorobenzotriazole(Compound 36), and this compound was added in an amount of 0.75 g (0.75%by weight with respect to the total weight of polymerizable compounds).

Comparative Example 15

A flat lens having a thickness of 2 mm was obtained by a method similarto that used in Example 71, except that Compound 36 of ComparativeExample 14 was added in an amount of 0.85 g (0.85% by weight withrespect to the total weight of polymerizable compounds).

Comparative Example 16

A flat lens having a thickness of 2 mm was obtained by a method similarto that used in Example 71, except that Compound 8 of Example 73 waschanged to 2-(2-hydroxy-3-t-butyl-5-methylphenyl)-chlorobenzotriazole(Compound 36), and this compound was added in an amount of 0.75 g (0.75%by weight with respect to the total weight of polymerizable compounds).

Comparative Example 17

A flat lens having a thickness of 2 mm was obtained by a method similarto that used in Example 71, except that Compound 8 of Example 74 waschanged to 2-(2-hydroxy-3-t-butyl-5-methylphenyl)-chlorobenzotriazole(Compound 36), and this compound was added in an amount of 0.50 g (0.50%by weight with respect to the total weight of polymerizable compounds).

Comparative Example 18

A flat lens having a thickness of 2 mm was obtained by a method similarto that used in Example 75, except that Compound 8 of Example 75 waschanged to 2-(2-hydroxy-3-t-butyl-5-methylphenyl)-chlorobenzotriazole(Compound 36), and this compound was added in an amount of 0.30 g (0.30%by weight with respect to the total weight of polymerizable compounds).

(1) Transmittance, Yellow Index (YI Value), and Visual Transmittance

For the sample lenses produced in Examples and Comparative Examples, thespectral transmittance for 350 to 800 nm, the yellow index (YI value),and the visual transmittance were measured using an ultraviolet-visiblespectrophotometer (U-4100 manufactured by Hitachi High-TechnologiesCorp.). The yellow index and the visual transmittance were determined asvalues obtained under the conditions of a 2-degree viewing field with aD65 light source.

(2) Evaluation of External Appearance of Sample Lenses

For the sample lenses thus produced, yellowness of the sample lenses ofExamples and Comparative Examples in which the transmittances for near420 nm in the same resin material were close to one another, wascompared and checked by visual inspection. It is because since theyellowness originally possessed by a resin itself varies depending onthe type of the resin, yellowness obtainable by adding an ultravioletabsorber cannot be accurately compared in different resins. The lensesused for comparison were specifically Example 71 with ComparativeExample 14, Example 72 with Comparative Example 15, Example 73 withComparative Example 16, Example 74 with Comparative Example 17, Example75 with Comparative example 18, Example 76 with Comparative Example 14,and Example 77 with Comparative Example 14. The external appearance wasevaluated by the following criteria. Furthermore, precipitation of theultraviolet absorber from the resin and transparency were checked byvisual inspection.

Yellowness . . . ◯: Closer to colorlessness, x: Yellow

The YI values and the results for external appearance are presented inTable 14, and the results for measuring transmission spectra arepresented in FIG. 10 to FIG. 16.

When it is attempted to cut wavelengths in the wavelength region of 400to 420 nm using an ultraviolet absorber, depending on the type of theultraviolet absorber, yellowing of the resin may occur, or theultraviolet absorber is precipitated out without being able to bedissolved in the resin of a plastic lens, so that the resin may beclouded. For example, it is described in JP 4334633 B1 that when anultraviolet absorber having a molecular weight of more than 360 is used,its degree of solubility in the raw material monomers is decreased, andthe ultraviolet absorber is precipitated out on the surface of a plasticlens even if the amount of incorporation is 5 parts by weight of less.It is also described that when the ultraviolet absorber is used in thelimit amount at which precipitation does not occur, a sufficientultraviolet absorption ability is not obtained, and it is difficult toobtain a plastic lens capable of sufficiently absorbing ultraviolet rayhaving a wavelength of 380 to 400 nm. However, in regard to theadditives of the present invention, it was confirmed that due to theirstructural features, despite that Compounds 8, 10 and 14 have molecularweights of more than 360 compared to the molecular weight of 316 ofCompound 36, the compounds satisfactorily dissolve in monomers similarlyto Compound 36, are not precipitated out on the surface of plasticlenses thus obtained, and manifest affinity to monomers and plasticlenses due to the structure of the ultraviolet absorber of the presentinvention.

Furthermore, a plastic lens using an ultraviolet absorber represented byFormula (I) absorbs light having a wavelength of 400 to 420 nm moreefficiently with a smaller amount of addition, compared to a lens using2-(2-hydroxy-3-t-butyl-5-methylphenyl)-chlorobenzotriazole. Thus, a lenswhich has satisfactory transmissibility for light having a wavelength ofnear 420 nm or longer while suppressing adverse effects to the eye,suppresses yellowing of a plastic lens, and has excellent externalappearance, was obtained.

Therefore, it was recognized that the additive of the present inventionhas satisfactory compatibility with a resin serving as a matrix, and cansufficiently exhibit performances such as ultraviolet absorption andimparting of a high refractive index while maintaining hightransparency.

TABLE 14 Comparative Comparative Comparative Example 71 Example 14Example 72 Example 15 Example 73 Example 16 Type of ultraviolet absorberCompound 8 Compound 36 Compound 8 Compound 36 Compound 8 Compound 36(Compound 1) (2-(2-hydroxy- (Compound 1) (2-(2-hydroxy- (Compound 1)(2-(2-hydroxy- 3-t-butyl-5- 3-t-butyl-5- 3-t-butyl-5- methylphenyl)-methylphenyl)- methylphenyl)- chlorobenzo- chlorobenzo- chlorobenzo-triazole) triazole) triazole) Proportion of addition of 0.49 0.75 0.530.85 0.53 0.75 ultraviolet absorber (%) Resin refractive index 1.60 1.601.60 1.60 1.60 1.60 410 nm transmittance (%) 0.9 1.3 1.0 1.1 1.0 1.2 415nm transmittance (%) 5.6 8.4 4.8 6.4 6.5 8.3 420 nm transmittance (%)29.0 29.8 26.4 26.2 31.5 30.0 425 nm transmittance (%) 58.7 55.8 56.752.8 60.8 56.1 430 nm transmittance (%) 77.0 73.9 75.7 71.8 77.6 73.8440 nm transmittance (%) 88.0 86.7 87.4 86.5 87.0 86.4 Luminoustransmittance (%) 89.8 89.4 90.2 90.0 89.4 89.4 (Transmittance at 425nm) − 29.7 26.0 30.3 26.6 29.2 26.1 (transmittance at 420 nm)(Transmittance at 425 nm) − 53.1 47.4 51.9 46.4 54.2 47.8 (transmittanceat 415 nm) [(Transmittance at 425 nm) − 53.1 47.4 51.9 46.4 54.2 47.8(transmittance at 415 nm)] × (resin refractive index − 0.6) YI 7.6 8.28.0 8.6 7.3 8.1 Comparison on coloration ◯ X ◯ X ◯ X (yellowing)Precipitation of ultraviolet Absent Absent Absent Absent Absent Absentabsorber from resin Transparent Transparent Transparent TransparentTransparent Transparent Comparative Comparative Example 74 Example 17Example 75 Example 18 Example 76 Example 77 Type of ultraviolet absorberCompound 8 Compound 36 Compound 8 Compound 36 Compound 10 Compound 14(Compound 1) (2-(2-hydroxy- (Compound 1) (2-(2-hydroxy- (Compound 2)(Compound 4) 3-t-butyl-5- 3-t butyl-5- methylphenyl)- methylphenyl)-chlorobenzo- chlorobenzo- triazole) triazole) Proportion of addition of0.27 0.50 0.23 0.30 0.56 0.58 ultraviolet absorber (%) Resin refractiveindex 1.67 1.67 1.76 1.76 1.60 1.60 410 nm transmittance (%) 0.9 1.1 0.70.9 0.8 1.0 415 nm transmittance (%) 4.9 6.7 2.3 5.8 6.1 7.7 420 nmtransmittance (%) 26.3 24.8 17.7 22.5 30.1 32.7 425 nm transmittance (%)54.4 49.7 46.9 46.2 58.8 60.3 430 nm transmittance (%) 72.6 68.8 67.864.7 76.0 76.6 440 nm transmittance (%) 84.7 84.1 81.5 79.8 87.0 86.5Luminous transmittance (%) 88.3 88.2 85.9 85.8 89.5 89.4 (Transmittanceat 425 nm) − 28.0 24.9 29.2 23.7 28.7 27.6 (transmittance at 420 nm)(Transmittance at 425 nm) − 49.4 43.0 44.6 40.4 52.7 52.6 (transmittanceat 415 nm) [(Transmittance at 425 nm) − 52.9 46.0 51.7 46.9 52.7 52.6(transmittance at 415 nm)] × (resin refractive index − 0.6) YI 8.5 9.310.0 10.8 7.9 7.7 Comparison on coloration ◯ X ◯ X ◯ ◯ (yellowing)Precipitation of ultraviolet Absent Absent Absent Absent Absent Absentabsorber from resin Transparent Transparent Transparent TransparentTransparent Transparent

4. Evaluation of Immobilization of Additive Having Reactive FunctionalGroup to Resin

0.022 g of an isocyanate (HC-210 manufactured by Nippon PolyurethaneIndustry Co., Ltd.), 0.078 g of a polyol (ON-H37 manufactured by NipponPolyurethane Industry Co., Ltd.), and 0.002 g of each compound ofCompounds 1 and 20 were uniformly mixed with 12 g of chloroform, andabout 1 mL of the mixture was spin coated on a glass substrate under theconditions of 1,500 rpm and 20 seconds. Subsequently, chloroform wasremoved in an oven at 45° C., and then the residue was heated for 3hours at 100° C. Thus, a urethane film was produced.

The film thus obtained was immersed in warm water at 70° C., and theabsorbance at the maximum absorption wavelength of Compound 1 or 20 wasmeasured at a certain interval of time.

[(Absorbance after 10 or 40 hours/initial absorbance)×100] wasdesignated as the absorbance retention ratio (%), and the absorbanceretention ratios after 10 hours and after 40 hours were measured for thecompounds of Examples 1 and 20. The film retained transparency, and thusthe absorbance retention ratio of the film exhibited values almost closeto the initial values.

2.5 g of methyl methacrylate, 0.05 g of Compound 17, and 10 g of tolueneand 10 g of methyl ethyl ketone (MEK) as solvents were introducedtogether with 0.025 g of 1,1′-azobis(cyclohexane-1-carbonitrile) as apolymerization initiator, and the mixture was stirred for one hour in anitrogen atmosphere. Subsequently, a polymerization reaction wasperformed at a reaction temperature of 88° C. to 91° C. in a state ofbeing heated to reflux for 10 hours. 250 g of MEK was added to thecopolymer solution thus obtained, and the solution was dropped from adropping funnel into 2,500 g of methanol over one hour. The crystals ofa copolymer were precipitated out. Next, filtration, purification, anddrying under reduced pressure were performed, and thus 2.12 g of amethacrylic resin was obtained.

0.10 g of the methacrylic resin thus obtained was heated to melt at 280°C., and then the resin was dropped on a slide glass substrate, quicklyspread thereon, and air-cooled. Thus, a film was produced.

The film thus obtained was immersed in warm water at 70° C., and theabsorbance at the maximum absorption wavelength of Compound 17 wasmeasured after 10 hours and after 40 hours. The absorbance retentionratios were measured in the same manner as described above. The filmretained transparency, and thus the absorbance retention ratio of thefilm exhibited values almost close to the initial values.

That is, it was confirmed that elution of the additives having areactive functional group into monomers or resins does not occur, theadditives and the monomers react with each other so that the additivesare immobilized in resins, the resins maintain transparency withoutbleedout of the additives, and the resins can be respectively maintainedthe functions of ultraviolet absorbency and imparting of a highrefractive index for a long period of time.

The invention claimed is:
 1. An additive represented by the followingFormula (II):

wherein: at least one of R^(1b) and R^(6b) represents a hydroxyl group,at least one of R^(1b) to R^(10b) represents a monovalentsulfur-containing group represented by the following Formula (ii-1), andeach of the other R^(1b) to R^(10b) represents a hydrogen atom:

R^(11b)

_(q)SH  (ii-1) wherein in Formula (ii-1), R^(11b) is a divalenthydrocarbon group having 12 or fewer carbon atoms; and q represents aninteger of 0 or
 1. 2. An additive represented by the following Formula(II):

wherein: R^(6b) represents a hydroxyl group, at least one of R^(1b),R^(2b), R^(4b), R^(5b), R^(7b), R^(8b), R^(9b) and R^(10b) represents amonovalent sulfur-containing group represented by the following Formula(ii-2), and each of the other R^(1b) to R^(10b) represents a hydrogenatom:

R^(12b)

_(r)S

R^(13b)—S

_(s)R^(14b)  (ii-2) wherein in Formula (ii-2), R^(12b) represents adivalent hydrocarbon group having 1 to 20 carbon atoms which may besubstituted with, interrupted at least any one of two terminals by orinterrupted a carbon-carbon bond by an oxygen-containing group; R^(13b)represents, or ifs is 2 or larger, R^(13b)'s each independentlyrepresent, a divalent hydrocarbon group having 1 to 20 carbon atomswhich may be substituted with, interrupted at least any one of twoterminals by or interrupted a carbon-carbon bond by an oxygen-containinggroup; R^(14b) represents a monovalent hydrocarbon group having 1 to 20carbon atoms which may be substituted with, interrupted a proximalterminal by or interrupted a carbon-carbon bond by an oxygen-containinggroup; the total number of carbon atoms of R¹², s units of R^(13b) andR^(14b) is 25 or less; r represents an integer of 0 or 1; and srepresents an integer from 0 to 3, and wherein the oxygen-containinggroup is selected from the group consisting of a hydroxyl group, amethoxy group, an ethoxy group, a propoxy group, a butoxy group, aphenoxy group, a methylphenoxy group, a dimethylphenoxy group, anaphthoxy group, a phenylmethoxy group, a phenylethoxy group, an acetoxygroup, an acetyl group, an aldehyde group, a carboxyl group, a carbamoylgroup, a urea group, an ether group, a carbonyl group, an ester group,an oxazole group and a morpholine group.
 3. The additive according toclaim 1, wherein R^(6b) represents a hydroxyl group, at least one ofR^(1b) to R^(5b) and R^(7b) to R^(10b) represents a monovalentsulfur-containing group represented by Formula (ii-1), and each of theother R^(1b) to R^(10b) represents a hydrogen atom.
 4. The additiveaccording to claim 1, wherein R^(6b) represents a hydroxyl group, atleast one of R^(7b) to R^(10b) represents a monovalent sulfur-containinggroup represented by Formula (ii-1), and each of the other R^(1b) toR^(10b) represents a hydrogen atom.
 5. The additive according to claim1, wherein R^(11b) is an alkylene group having 12 or fewer carbon atoms.6. The additive according to claim 3, wherein R^(11b) is an alkylenegroup having 12 or fewer carbon atoms.
 7. The additive according toclaim 4, wherein R^(11b) is an alkylene group having 12 or fewer carbonatoms.
 8. The additive according to claim 2, wherein R^(6b) represents ahydroxyl group, at least one of R^(7b) to R^(10b) represent a monovalentsulfur-containing group represented by Formula (ii-2), and each of theother R^(1b) to R^(10b) represents a hydrogen atom.
 9. The additiveaccording to claim 2, wherein R^(6b) represents a hydroxyl group, atleast one of R^(8b) and R^(9b) represent a monovalent sulfur-containinggroup represented by Formula (ii-2), and each of the other R^(1b) toR^(10b) represents a hydrogen atom.
 10. The additive according to claim2, wherein R^(12b) and s units of R^(13b) are a divalent hydrocarbongroup having 1 to 20 carbon atoms; and R^(14b) is a monovalenthydrocarbon group having 1 to 20 carbon atoms.
 11. The additiveaccording to claim 2, wherein R^(12b) and s units of R^(13b) are analkylene group having 18 or fewer carbon atoms, and R^(14b) is an alkylgroup having 18 or fewer carbon atoms.
 12. The additive according toclaim 8, wherein R^(12b) and s units of R^(13b) are a divalenthydrocarbon group having 1 to 20 carbon atoms; and R^(14b) is amonovalent hydrocarbon group having 1 to 20 carbon atoms.
 13. Theadditive according to claim 8, wherein R^(12b) and s units of R^(13b)are an alkylene group having 18 or fewer carbon atoms, and R^(14b) is analkyl group having 18 or fewer carbon atoms.
 14. The additive accordingto claim 9, wherein R^(12b) and s units of R^(13b) are a divalenthydrocarbon group having 1 to 20 carbon atoms; and R^(14b) is amonovalent hydrocarbon group having 1 to 20 carbon atoms.
 15. Theadditive according to claim 9, wherein R^(12b) and s units of R^(13b)are an alkylene group having 18 or fewer carbon atoms, and R^(14b) is analkyl group having 18 or fewer carbon atoms.